ACS Publications. Most Trusted. Most Cited. Most Read
CONTENT TYPES

Methylene-Bridged Bisphosphine Monoxide Ligands for Palladium-Catalyzed Copolymerization of Ethylene and Polar Monomers

  • Yusuke Mitsushige
    Yusuke Mitsushige
    Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Hina Yasuda
    Hina Yasuda
    Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    More by Hina Yasuda
  • Brad P. Carrow
    Brad P. Carrow
    Department of Chemistry, Princeton University, Princeton, New Jersey, United States
  • Shingo Ito
    Shingo Ito
    Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    More by Shingo Ito
  • Minoru Kobayashi
    Minoru Kobayashi
    Japan Polychem Corporation, 1 Toho-cho, Yokkaichi, Mie 510-0848, Japan
  • Takao Tayano
    Takao Tayano
    Japan Polychem Corporation, 1 Toho-cho, Yokkaichi, Mie 510-0848, Japan
    More by Takao Tayano
  • Yumiko Watanabe
    Yumiko Watanabe
    Computational Science and Technology Information Center, Showa Denko K.K., 1-1-1 Ohnodai, Midori-ku, Chiba, Chiba 267-0056, Japan
  • Yoshishige Okuno
    Yoshishige Okuno
    Computational Science and Technology Information Center, Showa Denko K.K., 1-1-1 Ohnodai, Midori-ku, Chiba, Chiba 267-0056, Japan
  • Shinya Hayashi
    Shinya Hayashi
    Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
  • Junichi Kuroda
    Junichi Kuroda
    Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
  • Yoshikuni Okumura
    Yoshikuni Okumura
    Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
  • , and 
  • Kyoko Nozaki*
    Kyoko Nozaki
    Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    *E-mail: [email protected]
    More by Kyoko Nozaki
Cite this: ACS Macro Lett. 2018, 7, 3, 305–311
Publication Date (Web):February 16, 2018
https://doi.org/10.1021/acsmacrolett.8b00034
Copyright © 2018 American Chemical Society
Subscribed Access
Article Views
2254
Altmetric
-
Citations
LEARN ABOUT THESE METRICS
PDF (1 MB) OpenURL UNIV OF HOUSTON MAIN
Supporting Info (1)»

Abstract

A series of palladium complexes bearing a bisphosphine monoxide with a methylene linker, that is, [κ2-P,O-(R12P)CH2P(O)R22]PdMe(2,6-lutidine)][BArF4] (Pd/BPMO), were synthesized and evaluated as catalysts for the homopolymerization of ethylene and the copolymerization of ethylene and polar monomers. X-ray crystallographic analyses revealed that these Pd/BPMO complexes exhibit significantly narrower bite angles and longer Pd–O bonds than Pd/BPMO complexes bearing a phenylene linker, while maintaining almost constant Pd–P bond lengths. Among the complexes synthesized, menthyl-substituted complex 3f (R1 = (1R,2S,5R)-2-isopropyl-5-methylcyclohexan-1-yl; R2 = Me) showed the best catalytic performance in the homo- and copolymerization in terms of molecular weight and polymerization activity. Meanwhile, complex 3e (R1 = t-Bu; R2 = Me) exhibited a markedly higher incorporation of comonomers in the copolymerization of ethylene and allyl acetate (≤12.0 mol %) or methyl methacrylate (≤0.6 mol %). The catalytic system represents one of the first examples of late-transition-metal complexes bearing an alkylene-bridged bidentate ligand that afford high-molecular-weight copolymers from the copolymerization of ethylene and polar monomers.

Given that the reactivity of homogeneous transition-metal catalysts depends not only on the metal center, but also largely on the nature of the ligands, the development of bespoke ligands is a central pillar of research in this area. In order to develop new ligands, the stereoelectronic effects of the ligands can be optimized by changing the type of coordination site, as well as substituents on or around the coordination site. In the case of bidentate ligands, the backbone structure of the ligand is also an important factor to modulate the distance between two coordination sites and the bite angle, which may influence the reactivity and selectivity of the catalysts.(1) The backbone structure of the ligand may also affect the electron-donating ability of bidentate ligands.(2) Thus, acquiring in-depth knowledge on the effect of the backbone structure on the catalytic performance is essential to the design of novel bidentate ligands for active and selective homogeneous transition-metal-based catalysts.

Intensive efforts have been devoted to the development of late-transition-metal-catalyzed copolymerizations of ethylene and polar monomers for synthesizing functional polyolefin materials; seminal discoveries in this area include palladium/α-diimine,(3,4) palladium/phosphine–sulfonate,(5−7) and palladium/IzQO catalysts.(8) Given that the latter two systems are able to copolymerize a wider range of comonomers, various bidentate ligands have been designed and synthesized in an attempt to mimic their unique structural features,(9) that is, electronically unsymmetric coordination sites consisting of a strong σ-donating group with bulky substituents and a weak σ-donating group. This unsymmetric structure is responsible for suppressing β-hydride elimination and subsequent chain-transfer, which leads to an increase in molecular weight of the resulting polymers.(10) In comparison, less attention has been focused on the backbone structure of the bidentate ligands. While almost all of the group-10-metal-based copolymerization catalysts bear an unsymmetric bidentate ligand with an arylene linker between the two coordination sites,(9,11) fewer examples of group-10-metal-based catalysts with an alkylene-bridged bidentate ligand that catalyzed (co)oligo- and polymerizations of ethylene are known:(9a,12) Notable examples include nickel/2-(di-tert-butylphosphino)-1-phenylethan-1-one catalysts for ethylene/methyl 10-undecenoate copolymerization,(13) and palladium/cyclopentane-1,2-diyl-bridged phosphine–sulfonate complexes for ethylene/methyl acrylate and ethylene/vinyl fluoride copolymerization.(14)

Our group has previously developed phenylene-bridged bisphosphine monoxide (BPMO) ligands of the type R12PC6H4PR22═O (R1 = i-Pr, Ph, 2-MeOC6H4, 2-CF3C6H4; R2 = t-Bu, i-Pr, Me), which can promote the palladium-catalyzed coordination–insertion copolymerization of ethylene with various polar monomers.(15) Further investigations on this ligand platform revealed that changing the ligand backbone significantly influences the catalytic performance. Herein we describe the synthesis of novel palladium/BPMO complexes that bear a methylene linker (Figure 1)(16) and their catalytic performance in the homopolymerization of ethylene and the copolymerization of ethylene and polar monomers. The introduction of bulky R1 groups, such as tert-butyl and menthyl, on the phosphine moiety is thereby essential to obtain high-molecular-weight (co)polymers.

Figure 1

Figure 1. Palladium complexes bearing phenylene- and methylene-bridged BPMO ligands.

Methylene-bridged BPMO ligands 1af were synthesized according to Scheme 1. Ligands 1ac and 1ef were obtained from reactions of the corresponding chlorophosphines (ClPR12) with the respective (phosphorylmethyl)lithium (LiCH2P(═O)R22) compounds that were prepared via the deprotonation of the corresponding methylphosphine oxides with alkyllithium (Scheme 1a). Ligand 1d was prepared by the monoxidation of bis(di-tert-butylphosphanyl)methane (Scheme 1b). A subsequent reaction between ligands 1af and PdMeCl(cod) afforded complexes 2af, which were purified by recrystallization (Scheme 1c). Finally, complexes 2af were converted to complexes 3af with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF4) in the presence of 2,6-lutidine.

Scheme 1

Scheme 1. Synthesis of Methylene-Bridged BPMO Ligands and Their Palladium Complexes

The structures of all these palladium complexes were characterized by multinuclear NMR spectroscopy, as well as mass spectrometry and/or elemental analysis. The molecular structures of 2c and 2f were moreover characterized by single-crystal X-ray diffraction analysis (Figure 2). For comparison, the corresponding palladium complex 4,(15a) which bears a phenylene-bridged BPMO ligand (R1 = i-Pr, R2 = t-Bu), is also shown in Figure 2c. The bite angles of complexes 2c (85.05(8)°) and 2f (88.41 (10)°) are narrower than that of complex 4 (91.19(6)°), which is consistent with the bite angles of well-known diphosphine ligands that form five-membered rings or six-membered rings (1,2-bis(diphenylphosphino)ethane: 85°; and 1,2-bis(diphenylphosphino)propane: 91°) upon chelation.(1b) The narrower bite angles of complexes 2c and 2f relative to complex 4 induces an elongation of the Pd1–O1 bond by about 0.11 Å. As a result, electron donation from the phosphine oxide moiety seems to be slightly weakened, which results in a contraction of the Pd1–C1 bond in 2c and 2f compared to that in 4. It is notable that the Pd1–P1 bond length and P1–Pd1–C1 angle are comparable in 2c, 2f, and 4. These results suggest that changing the backbone from phenylene to methylene modulates the environment around the phosphine oxide moiety electronically and sterically without changing the environment around the phosphine moiety.

Figure 2

Figure 2. X-ray structures of palladium/BPMO complexes (a) 2c, (b) 2f, and (c) 4 with 50% thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): (a) 2c: Pd1–P1 2.2054(13), Pd1–O1 2.236(3), Pd1–C1 2.033(5), P1–Pd1–O1 85.05(8), P1–Pd1–C1 92.33(14). (b) 2f: Pd1–P1 2.2188(16), Pd1–O1 2.224(5), Pd1–C1 2.027(7), P1–Pd1–O1 88.45(12), P1–Pd1–C1 91.55(18). (c) 4: Pd1–P1 2.2285(10), Pd1–O1 2.120(2), Pd1–C1 2.068(3), P1–Pd1–O1 91.19(6), P1–Pd1–C1 92.51(11).

Palladium complexes 3af were examined in the homopolymerization of ethylene (Table 1). Complexes 3a and 3b, which bear aryl groups on the phosphine moiety, exclusively afforded oligoethylenes, indicating inferior performance relative to the corresponding palladium complexes bearing a phenylene-bridged BPMO ligand (5a and 5b) (compare entries 1 and 2 with entries 7 and 8). Alkyl-substituted complex 3c also exhibited a poorer performance than the corresponding phenylene-bridged complex (5c; compare entries 3 and 9). Considering the X-ray structures of 2c and 4, this difference could arise from the change in the steric environment around the palladium center caused by the smaller bite angle of the methylene-bridged ligands. The decrease of “steric protection” is known to cause relatively faster β-hydride elimination followed by chain transfer leading ultimately in lower catalytic activity.(6b,c) It is noteworthy that 3a3c afforded highly linear polyethylenes with less than 1–4 methyl branches per 103 carbon atoms (entries 1–3), while complexes 5a5c afforded moderately branched polyethylenes (517 methyl branches per 103 carbon atoms, see entries 7–9). These results could be rationalized in terms of a fast chain transfer after the β-hydride elimination, as the formation of methyl-branched structures requires reinsertion of the formed alkene in the opposite direction after the β-hydride elimination. We therefore decided to increase the steric bulk around the phosphine moiety in order to suppress the chain transfer. When the R1 group was changed from isopropyl to tert-butyl, the molecular weight of the resulting polyethylene dramatically increased to Mn = 24 × 103 (entry 4). These results suggest that substituents on the phosphine moiety should be bulky to compensate for the decreased steric hindrance caused by the small bite angle in the case of methylene-bridged ligands. Further modification of the ligands revealed that changing the R2 group to methyl (3e) improved the catalytic activity and linearity compared to 3d, while maintaining the molecular weight (entry 5). This behavior stands in stark contrast to that discussed in our previous report, in which a decrease of molecular weight was observed upon changing the substituents on the phosphine oxide moiety from tert-butyl to methyl.(15b) Finally, complex 3f, which has menthyl groups on the phosphine moiety and methyl groups on the phosphine oxide moiety, exhibited the highest catalytic activity and linearity among complexes synthesized in this study (2,000 kg mol–1 h–1, < 1 methyl branch per 103 carbon atoms; entry 6).

Table 1. Homopolymerization of Ethylene by Palladium/BPMO Complexesa
entrycatalystyield (g)activity (kg mol–1 h–1)Mnb (103)Mw/MnbMe br.c (103 C)
13a0.709302.92.12
23b0.597902.32.11
33c0.101301.51.84
43d0.12160242.29
53e0.67890242.02
63f1.502000292.1<1
7d5a1.742300124.214
8d5b0.791100212.817
9d5c2.002700313.15
a

Conditions: ethylene (3.0 MPa) and catalyst (0.75 μmol) in toluene (15 mL) were stirred for 1 h at 100 °C in a 50 mL stainless autoclave.

b

Molecular weight determined by size-exclusion chromatography (SEC) analysis using polystyrene as an internal standard and calibrated by universal calibration.

c

Number of branched carbon atoms per 1000 carbon atoms determined by quantitative 13C NMR analysis.

d

Data from ref (15b).

With the best catalyst 3f in hand, the copolymerization of ethylene with various polar monomers was investigated (entries 1–10; Table 2). Copolymerization of ethylene (3.0 MPa) and allyl acetate (AAc; 20 vol % in toluene) at 80 °C afforded an ethylene/AAc copolymer with an AAc incorporation of 0.4 mol % (entry 1). When the concentration of AAc was increased to 80 vol % and the temperature was raised to 100 °C, the incorporation ratio of AAc increased almost 5-fold (2.1 mol %) as compared to that in entry 1 (entry 2). We subsequently explored the copolymerization of ethylene and polar monomers of the type CH2═CHOR, such as vinyl acetate (VAc) and butyl vinyl ether (BVE) (entries 3–8). Copolymers of ethylene and VAc or BVE were successfully obtained with incorporation ratios of 0.7–1.6 mol % of the polar monomer (entries 3–6). It should be noted that the incorporation ratio of BVE could be doubled under high-concentration conditions (compare entries 5 and 6). The catalyst system was also applied to acrylic monomers such as acrylonitrile (AN) and methyl acrylate (MA). The use of 20 vol % of AN at 80 °C resulted in the formation of polyethylene without any functional groups (entry 7); however, under high-concentration conditions, AN was successfully incorporated (1.0 mol %; entry 8). MA was also incorporated into the linear polyethylene, and the incorporation ratio could be increased 3-fold under high-concentration conditions (0.5 to 1.6 mol %; entries 9 and 10).

Table 2. Copolymerization of Ethylene and Polar Monomers by Palladium Complexes 3f and 3ea
entrycatalystpolar monomer (mL)toluene (mL)ethylene (MPa)temp (°C)yield (g)activity (kg mol–1 h–1)Mnb (103)Mw/Mnbincorp.c (mol %)
13fAAc (3.0)123.0800.795.3362.20.4
23fAAc (12)3.03.01000.392.69.52.02.1
33fVAc (12)3.03.0800.382.64.42.90.7
43fVAc (12)3.03.01000.473.13.12.30.7
53fBVE (3.0)123.0800.97d6.48.03.40.8
63fBVE (12)3.03.01000.37d2.59.01.91.6
73fAN (3.0)123.0800.966.43.72.20
83fAN (12)3.03.01000.100.71.01.61.0
93fMA (3.0)123.0803.120122.10.5
10e3fMA (12)3.03.01000.473.1152.61.6
113eAAc (1.0)143.0800.090.6102.11.4
123eAAc (2.0)133.0800.060.47.42.12.7
133eAAc (3.0)123.0800.060.46.32.03.2
143eAAc (5.0)103.0800.040.32.42.75.7
15f3eAAc (7.5)7.53.0800.050.21.52.88.6
16f,g3eAAc (12)3.03.0800.070.10.55.212.0
173eVAc (12)3.03.0800.120.81.21.92.7
183eAN (3.0)123.0800.271.83.12.30.3
19h3eMA (3.0)123.0800.030.20.91.97.2
20h3eMMA (3.0)122.01000.885.9102.70.1
21h3eMMA (12)3.02.01000.412.77.33.00.2
22h3eMMA (15)01.01000.090.62.24.00.6
a

Conditions: ethylene (1.0–3.0 MPa), 3f or 3e (10 μmol), and comonomer (x mL) in toluene (15–x mL) were stirred for 15 h at the indicated temperature in a 50 mL stainless steel autoclave. AAc: allyl acetate; VAc: vinyl acetate; BVE: butyl vinyl ether; AN: acrylonitrile; MA: methyl acrylate; MMA: methyl methacrylate.

b

Determined by SEC analysis using polystyrene as an internal standard and calibrated by universal calibration.

c

Incorporation ratio of polar monomer determined by 1H NMR or quantitative 13C NMR analysis.

d

Yield after Soxhlet extraction with chloroform in order to remove the BVE homopolymer.

e

50 μmol of galvinoxyl was added.

f

20 μmol of 3e was used.

g

Stirred for 36 h.

h

90 μmol of BHT was added.

During the investigation of the copolymerization, we serendipitously discovered a significant increase of comonomer incorporation efficiency when complex 3e was used as a catalyst (entries 11–22 in Table 2). First, we examined the copolymerization of ethylene and AAc using 3e (entries 11–16). As the concentration of AAc was increased from 6.7 to 80 vol %, the incorporation ratios also increased from 1.4 to 12.0 mol %. In order to compare the efficiency of the incorporation of AAc, we plotted the AAc incorporation ratios (mol %) as a function of the concentration of AAc (mol·L–1) divided by the pressure of ethylene (MPa), under the postulation that the amount of ethylene dissolved in the reaction mixture is linearly proportional to the pressure of ethylene and does not depend on the AAc:toluene ratio (Figure 3).(17) Solid blue and red lines represent the copolymerization results of 3e and 3f, respectively, while dotted green, orange, and purple lines represent those obtained from palladium/phosphine–sulfonate catalysts(7e,18) and palladium/phosphine-phosphinic amide catalyst.(9i) This comparison clearly shows that 3e can incorporate AAc more efficiently at 80 °C than any other of these palladium complexes with a [P–O]-type bidentate ligand. Notably, an incorporation ratio of 12.0 mol % AAc in the coordination–insertion copolymerization of ethylene is the highest value reported so far (entry 16). Subsequently, we carried out the copolymerization of ethylene with VAc, which resulted in the formation of a copolymer with an incorporation ratio of 2.7 mol % (entry 17), which represents the highest value among any other late-transition-metal-catalyzed ethylene/VAc copolymerizations reported to date. This catalytic system was also applied to the copolymerization of other polar monomers (entries 18–22). Complex 3e could incorporate 0.3 mol % of AN under low-concentration conditions (20 vol %); in contrast, no copolymer was obtained under the conditions when 3f was used as a catalyst (compare entries 7 and 18). Complex 3e moreover afforded a copolymer of ethylene and MA with a high incorporation ratio (7.2 mol %), albeit at the expense of low activity and molecular weight (entry 19). NMR analyses revealed that MA was incorporated mainly into the polymer main chain (78%) and into the polymer chain ends (22%).(19) Finally, the copolymerization of ethylene and MMA was examined (entries 20–22). Although many late-transition-metal complexes catalyze the copolymerization of ethylene and MMA,(20) very few catalysts produce statistical copolymers of ethylene and MMA.(8c) Complex 3e efficiently incorporated MMA into the main chain of polyethylenes with moderately high-molecular-weight (0.1 mol %, Mn = 10 × 103; entry 20). Under high-concentration conditions (80 vol %), incorporation ratio of MMA was doubled (0.2 mol %; entry 21), while reducing the ethylene pressure and increasing the MMA concentration (1.0 MPa, 100 vol %) resulted in the increase of the incorporation ratio of MMA to up to 0.6 mol % (entry 22). In our previous reports on successful formation of the statistical copolymer of ethylene and MMA,(8c) the unique capabilities of the palladium/IzQO catalyst allowed us to bridge the difference in the reactivities of ethylene and MMA (arising from differences in their steric demands). These differences prove to be detrimental in conventional systems. Along the same lines, the catalytic system in this work would also be expected to be insensitive toward different steric demands of different olefinic monomers.

Figure 3

Figure 3. Comparison of AAc incorporation ratios (mol %) as a function of the concentration of AAc (mol·L–1) divided by the pressure of ethylene (MPa) obtained from 3e, 3f, and other previously reported catalyst systems at 80 °C. Solid lines represent the results of this study, while dotted lines represent the results reported in ref (7e), (9i), and (18).

In conclusion, we have developed novel palladium/methylene-bridged BPMO catalysts, which successfully catalyze the copolymerization of ethylene and various polar monomers such as AAc, VAc, BVE, AN, MA, and MMA. The catalytic system represents one of the first examples of late-transition-metal complexes bearing a bidentate ligand bridged by an alkylene linker that are able to copolymerize ethylene with polar monomers. Catalyst 3f produces high-molecular-weight (co)polymers. Meanwhile, catalyst 3e exhibited higher incorporation efficiency than 3f, affording ethylene/AAc copolymers with AAc incorporations ratios of up to 12.0 mol %. Furthermore, complex 3e successfully incorporated MMA with an incorporation ratio of 0.6 mol %, thus representing the second example for the successful formation of a statistical ethylene/MMA copolymer. We are convinced that these insights into the effect of the ligand backbone structures on the ethylene homopolymerization and the ethylene/polar monomer copolymerization will benefit the future design of new functional polymeric materials.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsmacrolett.8b00034.

  • Experimental procedure, NMR spectra of complexes and (co)polymers, and X-ray crystallographic data (PDF).

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Author
  • Authors
    • Yusuke Mitsushige - Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
    • Hina Yasuda - Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanOrcidhttp://orcid.org/0000-0002-8770-0039
    • Brad P. Carrow - Department of Chemistry, Princeton University, Princeton, New Jersey, United StatesOrcidhttp://orcid.org/0000-0003-4929-8074
    • Shingo Ito - Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, JapanOrcidhttp://orcid.org/0000-0003-1776-4608
    • Minoru Kobayashi - Japan Polychem Corporation, 1 Toho-cho, Yokkaichi, Mie 510-0848, Japan
    • Takao Tayano - Japan Polychem Corporation, 1 Toho-cho, Yokkaichi, Mie 510-0848, Japan
    • Yumiko Watanabe - Computational Science and Technology Information Center, Showa Denko K.K., 1-1-1 Ohnodai, Midori-ku, Chiba, Chiba 267-0056, Japan
    • Yoshishige Okuno - Computational Science and Technology Information Center, Showa Denko K.K., 1-1-1 Ohnodai, Midori-ku, Chiba, Chiba 267-0056, Japan
    • Shinya Hayashi - Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
    • Junichi Kuroda - Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
    • Yoshikuni Okumura - Institute for Advanced and Core Technology, Showa Denko K.K., 2 Nakanosu, Oita, Oita 870-1809, Japan
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

ARTICLE SECTIONS
Jump To

This work was supported by JST, CREST, and “Nanotechnology Platform” (Project No.12024046) of MEXT, Japan. Y.M. is grateful to Program for Leading Graduate Schools (MERIT) from JSPS. S.I. is grateful for the financial support from Tonen General Sekiyu Foundation.

References

ARTICLE SECTIONS
Jump To

This article references 20 other publications.

  1. 1
    (a) Hartwig, J. F. Organotransition Metal Chemistry: From Bonding to Catalysis; University Science Books: Mill Valley, CA, 2009.
    (b) Dierkes, P.; van Leeuwen, P. W. N. M. The Bite Angle Makes the Difference: A Practical Ligand Parameter for Diphosphine Ligands. J. Chem. Soc., Dalton Trans. 1999, 15191529,  DOI: 10.1039/a807799a .
    (c) Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Reek, J. N. H. Wide Bite Angle Diphosphines: Xantphos Ligands in Transition Metal Complexes and Catalysis. Acc. Chem. Res. 2001, 34, 895904,  DOI: 10.1021/ar000060+
  2. 2
    Teng, Q.; Huynh, H. V. Determining the Electron-Donating Properties of Bidentate Ligands by 13C NMR Spectroscopy. Inorg. Chem. 2014, 53, 1096410973,  DOI: 10.1021/ic501325j
  3. 3
    (a) Johnson, L. K.; Killian, C. M.; Brookhart, M. New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and α-Olefins. J. Am. Chem. Soc. 1995, 117, 64146415,  DOI: 10.1021/ja00128a054 .
    (b) Killian, C. M.; Tempel, D. J.; Johnson, L. K.; Brookhart, M. Living Polymerization of α-Olefins Using NiII–α-Diimine Catalysts. Synthesis of New Block Polymers Based on α-Olefins. J. Am. Chem. Soc. 1996, 118, 1166411665,  DOI: 10.1021/ja962516h .
    (c) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and α-Olefins with Methyl Acrylate. J. Am. Chem. Soc. 1998, 120, 888899,  DOI: 10.1021/ja964144i .

    For review, see:

    (d) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Late-Metal Catalysts for Ethylene Homo- and Copolymerization. Chem. Rev. 2000, 100, 11691204,  DOI: 10.1021/cr9804644
  4. 4

    For recent examples, see:

    (a) Takano, S.; Takeuchi, D.; Osakada, K.; Akamatsu, N.; Shishido, A. Dipalladium Catalyst for Olefin Polymerization: Introduction of Acrylate Units into the Main Chain of Branched Polyethylene. Angew. Chem., Int. Ed. 2014, 53, 92469250,  DOI: 10.1002/anie.201404339 .
    (b) Allen, K. E.; Campos, J.; Daugulis, O.; Brookhart, M. Living Polymerization of Ethylene and Copolymerization of Ethylene/Methyl Acrylate Using “Sandwich” Diimine Palladium Catalysts. ACS Catal. 2015, 5, 456464,  DOI: 10.1021/cs5016029 .
    (c) Dai, S.; Sui, X.; Chen, C. Highly Robust Palladium(II) α-Diimine Catalysts for Slow-Chain-Walking Polymerization of Ethylene and Copolymerization with Methyl Acrylate. Angew. Chem., Int. Ed. 2015, 54, 99489953,  DOI: 10.1002/anie.201503708 .
    (d) Long, B. K.; Eagan, J. M.; Mulzer, M.; Coates, G. W. Semi-Crystalline Polar Polyethylene: Ester-Functionalized Linear Polyolefins Enabled by a Functional-Group-Tolerant, Cationic Nickel Catalyst. Angew. Chem., Int. Ed. 2016, 55, 71067110,  DOI: 10.1002/anie.201601703 .
    (e) Dai, S.; Zhou, S.; Zhang, W.; Chen, C. Systematic Investigations of Ligand Steric Effects on α-Diimine Palladium Catalyzed Olefin Polymerization and Copolymerization. Macromolecules 2016, 49, 88558862,  DOI: 10.1021/acs.macromol.6b02104 .
    (f) Dai, S.; Chen, C. Direct Synthesis of Functionalized High-Molecular-Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers. Angew. Chem., Int. Ed. 2016, 55, 1328113285,  DOI: 10.1002/anie.201607152 .
    (g) Chen, Z.; Liu, W.; Daugulis, O.; Brookhart, M. Mechanistic Studies of Pd(II)-Catalyzed Copolymerization of Ethylene and Vinylalkoxysilanes: Evidence for a β-Silyl Elimination Chain Transfer Mechanism. J. Am. Chem. Soc. 2016, 138, 1612016129,  DOI: 10.1021/jacs.6b10462 .
    (h) Zhao, M.; Chen, C. Accessing Multiple Catalytically Active States in Redox-Controlled Olefin Polymerization. ACS Catal. 2017, 7, 74907494,  DOI: 10.1021/acscatal.7b02564 .
    (i) Li, M.; Wang, X.; Luo, Y.; Chen, C. A Second-Coordination-Sphere Strategy to Modulate Nickel- and Palladium-Catalyzed Olefin Polymerization and Copolymerization. Angew. Chem., Int. Ed. 2017, 56, 1160411609,  DOI: 10.1002/anie.201706249
  5. 5
    Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I. Palladium Catalysed Copolymerisation of Ethene with Alkylacrylates: Polar Comonomer Built into the Linear Polymer Chain. Chem. Commun. 2002, 744745,  DOI: 10.1039/b111252j
  6. 6

    For review, see:

    (a) Berkefeld, A.; Mecking, S. Coordination Copolymerization of Polar Vinyl Monomers H2C═CHX. Angew. Chem., Int. Ed. 2008, 47, 25382542,  DOI: 10.1002/anie.200704642 .
    (b) Nakamura, A.; Ito, S.; Nozaki, K. Coordination–Insertion Copolymerization of Fundamental Polar Monomers. Chem. Rev. 2009, 109, 52155244,  DOI: 10.1021/cr900079r .
    (c) Ito, S.; Nozaki, K. Coordination–Insertion Copolymerization of Polar Vinyl Monomers by Palladium Catalysts. Chem. Rec. 2010, 10, 315325,  DOI: 10.1002/tcr.201000032 .
    (d) Nakamura, A.; Anselment, T. M. J.; Claverie, J. P.; Goodall, B.; Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W. N. M.; Nozaki, K. Ortho-Phosphinobenzenesulfonate: A Superb Ligand for Palladium-Catalyzed Coordination–Insertion Copolymerization of Polar Vinyl Monomers. Acc. Chem. Res. 2013, 46, 14381449,  DOI: 10.1021/ar300256h .
    (e) Carrow, B. P.; Nozaki, K. Transition-Metal-Catalyzed Functional Polyolefin Synthesis: Effecting Control through Chelating Ancillary Ligand Design and Mechanistic Insights. Macromolecules 2014, 47, 25412555,  DOI: 10.1021/ma500034g .
    (f) Guo, L.; Dai, S.; Sui, X.; Chen, C. Palladium and Nickel Catalyzed Chain Walking Olefin Polymerization and Copolymerization. ACS Catal. 2016, 6, 428441,  DOI: 10.1021/acscatal.5b02426
  7. 7

    For recent examples not included in ref (6d), see:

    (a) Leicht, H.; Göttker-Schnetmann, I.; Mecking, S. Incorporation of Vinyl Chloride in Insertion Polymerization. Angew. Chem., Int. Ed. 2013, 52, 39633966,  DOI: 10.1002/anie.201209724 .
    (b) Wucher, P.; Goldbach, V.; Mecking, S. Electronic Influences in Phosphinesulfonato Palladium(II) Polymerization Catalysts. Organometallics 2013, 32, 45164522,  DOI: 10.1021/om400297x .
    (c) Lanzinger, D.; Giuman, M. M.; Anselment, T. M. J.; Rieger, B. Copolymerization of Ethylene and 3,3,3-Trifluoropropene Using (Phosphine-sulfonate)Pd(Me)(DMSO) as Catalyst. ACS Macro Lett. 2014, 3, 931934,  DOI: 10.1021/mz5004344 .
    (d) Jian, Z.; Wucher, P.; Mecking, S. Heterocycle-Substituted Phosphinesulfonato Palladium(II) Complexes for Insertion Copolymerization of Methyl Acrylate. Organometallics 2014, 33, 28792888,  DOI: 10.1021/om500400a .
    (e) Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y.; Nozaki, K. Quantification of the Steric Influence of Alkylphosphine–Sulfonate Ligands on Polymerization, Leading to High-Molecular-Weight Copolymers of Ethylene and Polar Monomers. J. Am. Chem. Soc. 2014, 136, 1189811901,  DOI: 10.1021/ja505558e .
    (f) Jian, Z.; Baier, M. C.; Mecking, S. Suppression of Chain Transfer in Catalytic Acrylate Polymerization via Rapid and Selective Secondary Insertion. J. Am. Chem. Soc. 2015, 137, 28362839,  DOI: 10.1021/jacs.5b00179 .
    (g) Chen, M.; Yang, B.; Chen, C. Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes. Angew. Chem., Int. Ed. 2015, 54, 1552015524,  DOI: 10.1002/anie.201507274 .
    (h) Jian, Z.; Mecking, S. Insertion Homo- and Copolymerization of Diallyl Ether. Angew. Chem., Int. Ed. 2015, 54, 1584515849,  DOI: 10.1002/anie.201508930 .
    (i) Jian, Z.; Leicht, H.; Mecking, S. Direct Synthesis of Imidazolium-Functional Polyethylene by Insertion Copolymerization. Macromol. Rapid Commun. 2016, 37, 934938,  DOI: 10.1002/marc.201600073 .
    (j) Jian, Z.; Mecking, S. Short-Chain Branched Polar-Functionalized Linear Polyethylene via “Tandem Catalysis”. Macromolecules 2016, 49, 40574066,  DOI: 10.1021/acs.macromol.6b00581 .
    (k) Jian, Z.; Mecking, S. Insertion Polymerization of Divinyl Formal. Macromolecules 2016, 49, 43954403,  DOI: 10.1021/acs.macromol.6b00983 .
    (l) Ota, Y.; Ito, S.; Kobayashi, M.; Kitade, S.; Sakata, K.; Tayano, T.; Nozaki, K. Crystalline Isotactic Polar Polypropylene from the Palladium-Catalyzed Copolymerization of Propylene and Polar Monomers. Angew. Chem., Int. Ed. 2016, 55, 75057509,  DOI: 10.1002/anie.201600819 .
    (m) Wada, S.; Jordan, R., F. Olefin Insertion into a Pd–F Bond: Catalyst Reactivation Following β-F Elimination in Ethylene/Vinyl Fluoride Copolymerization. Angew. Chem., Int. Ed. 2017, 56, 18201824,  DOI: 10.1002/anie.201611198 .
    (n) Zhang, D.; Chen, C. Influence of Polyethylene Glycol Unit on Palladium- and Nickel-Catalyzed Ethylene Polymerization and Copolymerization. Angew. Chem., Int. Ed. 2017, 56, 1467214676,  DOI: 10.1002/anie.201708212
  8. 8
    (a) Nakano, R.; Nozaki, K. Copolymerization of Propylene and Polar Monomers Using Pd/IzQO Catalysts. J. Am. Chem. Soc. 2015, 137, 1093410937,  DOI: 10.1021/jacs.5b06948 .
    (b) Tao, W.; Nakano, R.; Ito, S.; Nozaki, K. Copolymerization of Ethylene and Polar Monomers by Using Ni/IzQO Catalysts. Angew. Chem., Int. Ed. 2016, 55, 28352839,  DOI: 10.1002/anie.201510077 .
    (c) Yasuda, H.; Nakano, R.; Ito, S.; Nozaki, K. Palladium/IzQO-Catalyzed Coordination–Insertion Copolymerization of Ethylene and 1,1-Disubstituted Ethylenes Bearing a Polar Functional Group. J. Am. Chem. Soc. 2018, 140, 18761883,  DOI: 10.1021/jacs.7b12593
  9. 9
    (a) Nagai, Y.; Kochi, T.; Nozaki, K. Synthesis of N-Heterocyclic Carbene-Sulfonate Palladium Complexes. Organometallics 2009, 28, 61316134,  DOI: 10.1021/om9004252 .
    (b) Zhou, X.; Jordan, R. F. Synthesis, cis/trans Isomerization, and Reactivity of Palladium Alkyl Complexes That Contain a Chelating N-Heterocyclic-Carbene Sulfonate Ligand. Organometallics 2011, 30, 46324642,  DOI: 10.1021/om200482a .
    (c) Gott, A. L.; Piers, W. E.; Dutton, J. L.; McDonald, R.; Parvez, M. Dimerization of Ethylene by Palladium Complexes Containing Bidentate Trifluoroborate-Functionalized Phosphine Ligands. Organometallics 2011, 30, 42364249,  DOI: 10.1021/om2004095 .
    (d) Kim, Y.; Jordan, R. F. Synthesis, Structures, and Ethylene Dimerization Reactivity of Palladium Alkyl Complexes That Contain a Chelating Phosphine–Trifluoroborate Ligand. Organometallics 2011, 30, 42504256,  DOI: 10.1021/om200472x .
    (e) Wucher, P.; Roesle, P.; Falivene, L.; Cavallo, L.; Caporaso, L.; Göttker-Schnetmann, I.; Mecking, S. Controlled Acrylate Insertion Regioselectivity in Diazaphospholidine-Sulfonato Palladium(II) Complexes. Organometallics 2012, 31, 85058515,  DOI: 10.1021/om300755j .
    (f) Contrella, N. D.; Sampson, J. R.; Jordan, R. F. Copolymerization of Ethylene and Methyl Acrylate by Cationic Palladium Catalysts That Contain Phosphine-Diethyl Phosphonate Ancillary Ligands. Organometallics 2014, 33, 35463555,  DOI: 10.1021/om5004489 .
    (g) Zhang, Y.; Cao, Y.; Leng, X.; Chen, C.; Huang, Z. Cationic Palladium(II) Complexes of Phosphine–Sulfonamide Ligands: Synthesis, Characterization, and Catalytic Ethylene Oligomerization. Organometallics 2014, 33, 37383745,  DOI: 10.1021/om5004094 .
    (h) Jian, Z.; Falivene, L.; Wucher, P.; Roesle, P.; Caporaso, L.; Cavallo, L.; Göttker-Schnetmann, I.; Mecking, S. Insights into Functional-Group-Tolerant Polymerization Catalysis with Phosphine–Sulfonamide Palladium(II) Complexes. Chem. - Eur. J. 2015, 21, 20622075,  DOI: 10.1002/chem.201404856 .
    (i) Sui, X.; Dai, S.; Chen, C. Ethylene Polymerization and Copolymerization with Polar Monomers by Cationic Phosphine Phosphonic Amide Palladium Complexes. ACS Catal. 2015, 5, 59325937,  DOI: 10.1021/acscatal.5b01490
  10. 10
    (a) Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. Mechanistic Studies on the Formation of Linear Polyethylene Chain Catalyzed by Palladium Phosphine–Sulfonate Complexes: Experiment and Theoretical Studies. J. Am. Chem. Soc. 2009, 131, 1408814100,  DOI: 10.1021/ja9047398 .
    (b) Nakano, R.; Chung, L. W.; Watanabe, Y.; Okuno, Y.; Okumura, Y.; Ito, S.; Morokuma, K.; Nozaki, K. Elucidating the Key Role of Phosphine–Sulfonate Ligands in Palladium-Catalyzed Ethylene Polymerization: Effect of Ligand Structure on the Molecular Weight and Linearity of Polyethylene. ACS Catal. 2016, 6, 61016113,  DOI: 10.1021/acscatal.6b00911
  11. 11
    Wu, Z.; Chen, M.; Chen, C. Ethylene Polymerization and Copolymerization by Palladium and Nickel Catalysts Containing Naphthalene-Bridged Phosphine–Sulfonate Ligands. Organometallics 2016, 35, 14721479,  DOI: 10.1021/acs.organomet.6b00076
  12. 12
    (a) Murry, R. E. U.S. Patent 4,689,437. Aug 25, 1987.
    (b) van Doorn, J. A.; Drent, E.; van Leeuwen, P. W. M. N.; Meijboon, N.; van Oort, A. B.; Wife, R. L. Eur. Pat. Appl. 0,280,380, Aug 31, 1988.
    (c) Keim, W.; Maas, H.; Mecking, S. Palladium Catalyzed Alternating Cooligomerization of Ethylene and Carbon Monoxide to Unsaturated Ketones. Z. Naturforsch., B: J. Chem. Sci. 1995, 50, 430438,  DOI: 10.1515/znb-1995-0318 .
    (d) Bennett, J. L.; Brookhart, M.; Johnson, L. K.; PCT Int. Appl. WO199830610, July 16, 1998.
    (e) Brassat, I.; Keim, W.; Killat, S.; Möthrath, M.; Mastrorilli, P.; Nobile, C. F.; Suranna, G. P. Synthesis and Catalytic Activity of Allyl, Methallyl and Methyl Complexes of Nickel(II) and Palladium(II) with Biphosphine Monoxide Ligands: Oligomerization of Ethylene and Copolymerization of Ethylene and Carbon Monoxide. J. Mol. Catal. A: Chem. 2000, 157, 4158,  DOI: 10.1016/S1381-1169(99)00449-5 .
    (f) Malinoski, J. M.; Brookhart, M. Polymerization and Oligomerization of Ethylene by Cationic Nickel(II) and Palladium(II) Complexes Containing Bidentate Phenacyldiarylphosphine Ligands. Organometallics 2003, 22, 53245335,  DOI: 10.1021/om030388h .
    (g) Bettucci, L.; Bianchini, C.; Claver, C.; Suarez, E. J. G.; Ruiz, A.; Meli, A.; Oberhauser, W. Ligand Effects in the Non-alternating CO–Ethylene Copolymerization by Palladium(II) Catalysis. Dalton Trans. 2007, 55905602,  DOI: 10.1039/b711280g
  13. 13
    Liu, W.; Malinoski, J. M.; Brookhart, M. Ethylene Polymerization and Ethylene/Methyl 10-Undecenoate Copolymerization Using Nickel(II) and Palladium(II) Complexes Derived from a Bulky P,O Chelating Ligand. Organometallics 2002, 21, 28362838,  DOI: 10.1021/om0201516
  14. 14
    Black, R. E.; Jordan, R. F. Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands. Organometallics 2017, 36, 34153428,  DOI: 10.1021/acs.organomet.7b00572
  15. 15
    (a) Carrow, B. P.; Nozaki, K. Synthesis of Functional Polyolefins Using Cationic Bisphosphine Monoxide–Palladium Complexes. J. Am. Chem. Soc. 2012, 134, 88028805,  DOI: 10.1021/ja303507t .
    (b) Mitsushige, Y.; Carrow, B. P.; Ito, S.; Nozaki, K. Ligand-Controlled Insertion Regioselectivity Accelerates Copolymerisation of Ethylene with Methyl Acrylate by Cationic Bisphosphine Monoxide–Palladium Catalysts. Chem. Sci. 2016, 7, 737744,  DOI: 10.1039/C5SC03361F
  16. 16
    A part of the present work has already been disclosed in a patent, see:Nozaki, K.; Carrow, B. P.; Okumura, Y.; Kuroda, J. WO2013168626, 2013.
  17. 17
    The amount of ethylene dissolved in toluene does not linearly correlate with the pressure of ethylene, especially when the pressure of ethylene is <0.5 MPa; see:Schuster, N.; Rünzi, T.; Mecking, S. Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization. Macromolecules 2016, 49, 11721179,  DOI: 10.1021/acs.macromol.5b02749
  18. 18
    Ito, S.; Kanazawa, M.; Munakata, K.; Kuroda, J.; Okumura, Y.; Nozaki, K. Coordination–Insertion Copolymerization of Allyl Monomers with Ethylene. J. Am. Chem. Soc. 2011, 133, 12321235,  DOI: 10.1021/ja1092216
  19. 19

    For details, see Figure S63 in the Supporting Information.

  20. 20
    There are several types of ethylene/MMA copolymers formed via late transition metal catalysis: (1) ethylene/MMA copolymers featuring chain-end incorporation of MMA formed via coordination–insertion mechanism (for the recent example, see:Chen, M.; Chen, C. A Versatile Ligand Platform for Palladium- and Nickel-catalyzed Ethylene Copolymerizations with Polar Monomers. Angew. Chem., Int. Ed. 2018, in press. DOI:  DOI: 10.1002/anie.201711753 ); (2) multiblock ethylene/MMA copolymers by a combination of coordination–insertion and radical mechanisms; (3) ethylene/MMA copolymers which might include consecutive polyMMA units formed by the intermediacy of radical-related processes. For the details, see ref (8c) and references cited therein.

Cited By


This article is cited by 47 publications.

  1. Shuoyan Xiong, Manar M. Shoshani, Xinglong Zhang, Heather A. Spinney, Alex J. Nett, Briana S. Henderson, Thomas F. Miller, III, Theodor Agapie. Efficient Copolymerization of Acrylate and Ethylene with Neutral P, O-Chelated Nickel Catalysts: Mechanistic Investigations of Monomer Insertion and Chelate Formation. Journal of the American Chemical Society 2021, 143 (17) , 6516-6527. https://doi.org/10.1021/jacs.1c00566OpenURL UNIV OF HOUSTON MAIN
  2. Philip B. V. Scholten, Grégory Cartigny, Bruno Grignard, Antoine Debuigne, Henri Cramail, Michael A. R. Meier, Christophe Detrembleur. Functional Polyethylenes by Organometallic-Mediated Radical Polymerization of Biobased Carbonates. ACS Macro Letters 2021, 10 (3) , 313-320. https://doi.org/10.1021/acsmacrolett.1c00037OpenURL UNIV OF HOUSTON MAIN
  3. Xu-ling Wang, Yan-ping Zhang, Fei Wang, Li Pan, Bin Wang, Yue-sheng Li. Robust and Reactive Neutral Nickel Catalysts for Ethylene Polymerization and Copolymerization with a Challenging 1,1-Disubstituted Difunctional Polar Monomer. ACS Catalysis 2021, 11 (5) , 2902-2911. https://doi.org/10.1021/acscatal.0c04450OpenURL UNIV OF HOUSTON MAIN
  4. Yuxing Zhang, Zhongbao Jian. Comprehensive Picture of Functionalized Vinyl Monomers in Chain-Walking Polymerization. Macromolecules 2020, 53 (20) , 8858-8866. https://doi.org/10.1021/acs.macromol.0c01953OpenURL UNIV OF HOUSTON MAIN
  5. Da-Ae Park, Seunghwan Byun, Ji Yeon Ryu, Jinyoung Lee, Junseong Lee, Sukwon Hong. Abnormal N-Heterocyclic Carbene–Palladium Complexes for the Copolymerization of Ethylene and Polar Monomers. ACS Catalysis 2020, 10 (10) , 5443-5453. https://doi.org/10.1021/acscatal.0c00802OpenURL UNIV OF HOUSTON MAIN
  6. Jin Jung, Hina Yasuda, Kyoko Nozaki. Copolymerization of Nonpolar Olefins and Allyl Acetate Using Nickel Catalysts Bearing a Methylene-Bridged Bisphosphine Monoxide Ligand. Macromolecules 2020, 53 (7) , 2547-2556. https://doi.org/10.1021/acs.macromol.0c00183OpenURL UNIV OF HOUSTON MAIN
  7. Ruining Shang, Huan Gao, Faliang Luo, Yulian Li, Bin Wang, Zhe Ma, Li Pan, Yuesheng Li. Functional Isotactic Polypropylenes via Efficient Direct Copolymerizations of Propylene with Various Amino-Functionalized α-Olefins. Macromolecules 2019, 52 (23) , 9280-9290. https://doi.org/10.1021/acs.macromol.9b00757OpenURL UNIV OF HOUSTON MAIN
  8. Dylan J. Walsh, Michael G. Hyatt, Susannah A. Miller, Damien Guironnet. Recent Trends in Catalytic Polymerizations. ACS Catalysis 2019, 9 (12) , 11153-11188. https://doi.org/10.1021/acscatal.9b03226OpenURL UNIV OF HOUSTON MAIN
  9. Anna Dall’Anese, Vera Rosar, Luca Cusin, Tiziano Montini, Gabriele Balducci, Ilaria D’Auria, Claudio Pellecchia, Paolo Fornasiero, Fulvia Felluga, Barbara Milani. Palladium-Catalyzed Ethylene/Methyl Acrylate Copolymerization: Moving from the Acenaphthene to the Phenanthrene Skeleton of α-Diimine Ligands. Organometallics 2019, 38 (19) , 3498-3511. https://doi.org/10.1021/acs.organomet.9b00308OpenURL UNIV OF HOUSTON MAIN
  10. Jie Dong, Minliang Li, Baiquan Wang. Synthesis, Structures, and Norbornene Polymerization Behavior of Imidazo[1,5-a]pyridine-sulfonate-Ligated Palladacycles. Organometallics 2019, 38 (19) , 3786-3795. https://doi.org/10.1021/acs.organomet.9b00495OpenURL UNIV OF HOUSTON MAIN
  11. Changwen Hong, Xingbao Wang, Changle Chen. Palladium-Catalyzed Dimerization of Vinyl Ethers: Mechanism, Catalyst Optimization, and Polymerization Applications. Macromolecules 2019, 52 (18) , 7123-7129. https://doi.org/10.1021/acs.macromol.9b01484OpenURL UNIV OF HOUSTON MAIN
  12. Junhao Ye, Hongliang Mu, Zhen Wang, Zhongbao Jian. Heteroaryl Backbone Strategy in Bisphosphine Monoxide Palladium-Catalyzed Ethylene Polymerization and Copolymerization with Polar Monomers. Organometallics 2019, 38 (15) , 2990-2997. https://doi.org/10.1021/acs.organomet.9b00340OpenURL UNIV OF HOUSTON MAIN
  13. Jiajie Sun, Min Chen, Gen Luo, Changle Chen, Yi Luo. Diphosphazane-monoxide and Phosphine-sulfonate Palladium Catalyzed Ethylene Copolymerization with Polar Monomers: A Computational Study. Organometallics 2019, 38 (3) , 638-646. https://doi.org/10.1021/acs.organomet.8b00796OpenURL UNIV OF HOUSTON MAIN
  14. Qian Liu, Richard F. Jordan. Multinuclear Palladium Olefin Polymerization Catalysts Based on Self-Assembled Zinc Phosphonate Cages. Organometallics 2018, 37 (24) , 4664-4674. https://doi.org/10.1021/acs.organomet.8b00683OpenURL UNIV OF HOUSTON MAIN
  15. Zhongzheng Cai, Loi H. Do. Thermally Robust Heterobimetallic Palladium–Alkali Catalysts for Ethylene and Alkyl Acrylate Copolymerization. Organometallics 2018, 37 (21) , 3874-3882. https://doi.org/10.1021/acs.organomet.8b00561OpenURL UNIV OF HOUSTON MAIN
  16. Shengyu Dai, Changle Chen. Palladium-Catalyzed Direct Synthesis of Various Branched, Carboxylic Acid-Functionalized Polyolefins: Characterization, Derivatization, and Properties. Macromolecules 2018, 51 (17) , 6818-6824. https://doi.org/10.1021/acs.macromol.8b01261OpenURL UNIV OF HOUSTON MAIN
  17. Shumpei Akita, Ryo Nakano, Shingo Ito, Kyoko Nozaki. Synthesis and Reactivity of Methylpalladium Complexes Bearing a Partially Saturated IzQO Ligand. Organometallics 2018, 37 (14) , 2286-2296. https://doi.org/10.1021/acs.organomet.8b00263OpenURL UNIV OF HOUSTON MAIN
  18. Wei Zhang, Peter M. Waddell, Margaret A. Tiedemann, Christian E. Padilla, Jiajun Mei, Liye Chen, Brad P. Carrow. Electron-Rich Metal Cations Enable Synthesis of High Molecular Weight, Linear Functional Polyethylenes. Journal of the American Chemical Society 2018, 140 (28) , 8841-8850. https://doi.org/10.1021/jacs.8b04712OpenURL UNIV OF HOUSTON MAIN
  19. Daniela E. Ortega. Theoretical Insight into the Effect of Fluorine‐Functionalized Metal‐Organic Framework Supported Palladium Single‐Site Catalyst in the Ethylene Dimerization Reaction. Chemistry – A European Journal 2021, 27 (40) , 10413-10421. https://doi.org/10.1002/chem.202101072OpenURL UNIV OF HOUSTON MAIN
  20. Guanglin Zhou, Lei Cui, Hongliang Mu, Zhongbao Jian. Custom-made polar monomers utilized in nickel and palladium promoted olefin copolymerization. Polymer Chemistry 2021, 12 (27) , 3878-3892. https://doi.org/10.1039/D1PY00492AOpenURL UNIV OF HOUSTON MAIN
  21. Hongliang Mu, Guanglin Zhou, Xiaoqiang Hu, Zhongbao Jian. Recent advances in nickel mediated copolymerization of olefin with polar monomers. Coordination Chemistry Reviews 2021, 435 , 213802. https://doi.org/10.1016/j.ccr.2021.213802OpenURL UNIV OF HOUSTON MAIN
  22. Rajkumar S. Birajdar, Samir H. Chikkali. Insertion copolymerization of functional olefins: Quo Vadis?. European Polymer Journal 2021, 143 , 110183. https://doi.org/10.1016/j.eurpolymj.2020.110183OpenURL UNIV OF HOUSTON MAIN
  23. Lei Cui, Zhongbao Jian. A N-bridged strategy enables hemilabile phosphine–carbonyl palladium and nickel catalysts to mediate ethylene polymerization and copolymerization with polar vinyl monomers. Polymer Chemistry 2020, 11 (38) , 6187-6193. https://doi.org/10.1039/D0PY01106AOpenURL UNIV OF HOUSTON MAIN
  24. Ce Liang, Jimin Yang, Gen Luo, Yi Luo. Benchmark study of density functionals for the insertions of olefin and polar monomers catalyzed by α–diimine palladium complexes. Computational and Theoretical Chemistry 2020, 1187 , 112942. https://doi.org/10.1016/j.comptc.2020.112942OpenURL UNIV OF HOUSTON MAIN
  25. Andleeb Mehmood, Xiaowei Xu, Waseem Raza, Ki-Hyun Kim, Yi Luo. Mechanistic Studies for Palladium Catalyzed Copolymerization of Ethylene with Vinyl Ethers. Polymers 2020, 12 (10) , 2401. https://doi.org/10.3390/polym12102401OpenURL UNIV OF HOUSTON MAIN
  26. Takayoshi YAMADA, Daisuke TAKEUCHI, Kohtaro OSAKADA, Ichihiro ARATANI. Copolymerization of 1-Decene with Alkyl and Alkenyl Methacrylates Catalyzed by Palladium–diimine Complexes. Journal of the Japan Petroleum Institute 2020, 63 (5) , 282-288. https://doi.org/10.1627/jpi.63.282OpenURL UNIV OF HOUSTON MAIN
  27. Evgueni Kirillov, Konstantin Rodygin, Valentine Ananikov. Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers. European Polymer Journal 2020, 136 , 109872. https://doi.org/10.1016/j.eurpolymj.2020.109872OpenURL UNIV OF HOUSTON MAIN
  28. Hong-Liang Mu, Jun-Hao Ye, Guang-Lin Zhou, Kang-Kang Li, Zhong-Bao Jian. Ethylene Polymerization and Copolymerization with Polar Monomers by Benzothiophene-bridged BPMO-Pd Catalysts. Chinese Journal of Polymer Science 2020, 38 (6) , 579-586. https://doi.org/10.1007/s10118-020-2359-0OpenURL UNIV OF HOUSTON MAIN
  29. Kangkang Li, Junhao Ye, Zhen Wang, Hongliang Mu, Zhongbao Jian. Indole-bridged bisphosphine-monoxide palladium catalysts for ethylene polymerization and copolymerization with polar monomers. Polymer Chemistry 2020, 11 (15) , 2740-2748. https://doi.org/10.1039/D0PY00100GOpenURL UNIV OF HOUSTON MAIN
  30. Yixin Zhang, Zhongbao Jian. 2-Phosphine-pyridine-N-oxide palladium and nickel catalysts for ethylene polymerization and copolymerization with polar monomers. Polymer 2020, 194 , 122410. https://doi.org/10.1016/j.polymer.2020.122410OpenURL UNIV OF HOUSTON MAIN
  31. Qitong Wu, Wenbing Wang, Guoyong Xu, Wenmin Pang, Yougui Li, Chen Tan, Fuzhou Wang. Bulky iminophosphine‐based nickel and palladium catalysts bearing 2,6‐dibenzhydryl groups for ethylene oligo‐/polymerization. Applied Organometallic Chemistry 2020, 34 (3) https://doi.org/10.1002/aoc.5428OpenURL UNIV OF HOUSTON MAIN
  32. Guanglin Zhou, Hongliang Mu, Zhongbao Jian. A comprehensive picture on catalyst structure construction in palladium catalyzed ethylene (co)polymerizations. Journal of Catalysis 2020, 383 , 215-220. https://doi.org/10.1016/j.jcat.2020.01.032OpenURL UNIV OF HOUSTON MAIN
  33. Satej S. Deshmukh, Shahaji R. Gaikwad, Rajesh G. Gonnade, Satish P. Pandole, Samir H. Chikkali. Pd‐Iminocarboxylate Complexes and Their Behavior in Ethylene Polymerization. Chemistry – An Asian Journal 2020, 15 (3) , 398-405. https://doi.org/10.1002/asia.201901501OpenURL UNIV OF HOUSTON MAIN
  34. Dawei Xiao, Zhongzheng Cai, Loi H. Do. Accelerating ethylene polymerization using secondary metal ions in tetrahydrofuran. Dalton Transactions 2019, 48 (48) , 17887-17897. https://doi.org/10.1039/C9DT04288AOpenURL UNIV OF HOUSTON MAIN
  35. Chen Zou, Chen Tan, Wenmin Pang, Changle Chen. Amidine/Phosphine‐Oxide‐Based Nickel Catalysts for Ethylene Polymerization and Copolymerization. ChemCatChem 2019, 11 (21) , 5339-5344. https://doi.org/10.1002/cctc.201901114OpenURL UNIV OF HOUSTON MAIN
  36. Guohong Wang, Min Li, Wenmin Pang, Min Chen, Chen Tan. Lewis acids in situ modulate pyridazine-imine Ni catalysed ethylene (co)polymerisation. New Journal of Chemistry 2019, 43 (34) , 13630-13634. https://doi.org/10.1039/C9NJ01243EOpenURL UNIV OF HOUSTON MAIN
  37. Chen Tan, Changle Chen. Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers. Angewandte Chemie 2019, 131 (22) , 7268-7276. https://doi.org/10.1002/ange.201814634OpenURL UNIV OF HOUSTON MAIN
  38. Chen Tan, Changle Chen. Emerging Palladium and Nickel Catalysts for Copolymerization of Olefins with Polar Monomers. Angewandte Chemie International Edition 2019, 58 (22) , 7192-7200. https://doi.org/10.1002/anie.201814634OpenURL UNIV OF HOUSTON MAIN
  39. Fuzhou Wang, Changle Chen. A continuing legend: the Brookhart-type α-diimine nickel and palladium catalysts. Polymer Chemistry 2019, 10 (19) , 2354-2369. https://doi.org/10.1039/C9PY00226JOpenURL UNIV OF HOUSTON MAIN
  40. Xiaoqiang Hu, Xin Ma, Zhongbao Jian. Coordination–insertion polymerization of polar allylbenzene monomers. Polymer Chemistry 2019, 10 (15) , 1912-1919. https://doi.org/10.1039/C9PY00026GOpenURL UNIV OF HOUSTON MAIN
  41. Susu Tian, Yang Zhang, Ruiping Li, Fuzhou Wang, Weimin Li. Cationic para-benzhydryl substituted α-diimine nickel catalyzed ethylene and 1-decene polymerizations via controllable chain-walking. Inorganica Chimica Acta 2019, 486 , 492-498. https://doi.org/10.1016/j.ica.2018.11.004OpenURL UNIV OF HOUSTON MAIN
  42. Ruiping Li, Jinlong Sun, Susu Tian, Yang Zhang, Dengfeng Guo, Weimin Li, Fuzhou Wang. Synthesis of highly branched polyethylene using para-benzhydryl substituted iminopyridyl Ni(II) and Pd(II) complexes. Journal of Organometallic Chemistry 2019, 880 , 261-266. https://doi.org/10.1016/j.jorganchem.2018.11.024OpenURL UNIV OF HOUSTON MAIN
  43. Jiaxin Gao, Bangpei Yang, Changle Chen. Sterics versus electronics: Imine/phosphine-oxide-based nickel catalysts for ethylene polymerization and copolymerization. Journal of Catalysis 2019, 369 , 233-238. https://doi.org/10.1016/j.jcat.2018.11.007OpenURL UNIV OF HOUSTON MAIN
  44. Guifu Si, Yinna Na, Changle Chen. Ethylene (co)Oligomerization by Phosphine‐Pyridine Based Palladium and Nickel Catalysts. ChemCatChem 2018, 10 (22) , 5135-5140. https://doi.org/10.1002/cctc.201800957OpenURL UNIV OF HOUSTON MAIN
  45. Lin Ding, Hailong Cheng, Yanqing Li, Ryo Tanaka, Takeshi Shiono, Zhengguo Cai. Efficient ethylene copolymerization with polar monomers using palladium anilinonaphthoquinone catalysts. Polymer Chemistry 2018, 9 (45) , 5476-5482. https://doi.org/10.1039/C8PY01292JOpenURL UNIV OF HOUSTON MAIN
  46. Shingo Ito. Effect of the backbone structure of bidentate ligands in palladium- and nickel-catalyzed polar monomer copolymerization. Science China Chemistry 2018, 61 (11) , 1349-1350. https://doi.org/10.1007/s11426-018-9317-5OpenURL UNIV OF HOUSTON MAIN
  47. Jun Fang, Xuelin Sui, Yougui Li, Changle Chen. Synthesis of polyolefin elastomers from unsymmetrical α-diimine nickel catalyzed olefin polymerization. Polymer Chemistry 2018, 9 (30) , 4143-4149. https://doi.org/10.1039/C8PY00725JOpenURL UNIV OF HOUSTON MAIN
  • Abstract

    Figure 1

    Figure 1. Palladium complexes bearing phenylene- and methylene-bridged BPMO ligands.

    Scheme 1

    Scheme 1. Synthesis of Methylene-Bridged BPMO Ligands and Their Palladium Complexes

    Figure 2

    Figure 2. X-ray structures of palladium/BPMO complexes (a) 2c, (b) 2f, and (c) 4 with 50% thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and angles (°): (a) 2c: Pd1–P1 2.2054(13), Pd1–O1 2.236(3), Pd1–C1 2.033(5), P1–Pd1–O1 85.05(8), P1–Pd1–C1 92.33(14). (b) 2f: Pd1–P1 2.2188(16), Pd1–O1 2.224(5), Pd1–C1 2.027(7), P1–Pd1–O1 88.45(12), P1–Pd1–C1 91.55(18). (c) 4: Pd1–P1 2.2285(10), Pd1–O1 2.120(2), Pd1–C1 2.068(3), P1–Pd1–O1 91.19(6), P1–Pd1–C1 92.51(11).

    Figure 3

    Figure 3. Comparison of AAc incorporation ratios (mol %) as a function of the concentration of AAc (mol·L–1) divided by the pressure of ethylene (MPa) obtained from 3e, 3f, and other previously reported catalyst systems at 80 °C. Solid lines represent the results of this study, while dotted lines represent the results reported in ref (7e), (9i), and (18).

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 20 other publications.

    1. 1
      (a) Hartwig, J. F. Organotransition Metal Chemistry: From Bonding to Catalysis; University Science Books: Mill Valley, CA, 2009.
      (b) Dierkes, P.; van Leeuwen, P. W. N. M. The Bite Angle Makes the Difference: A Practical Ligand Parameter for Diphosphine Ligands. J. Chem. Soc., Dalton Trans. 1999, 15191529,  DOI: 10.1039/a807799a .
      (c) Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Reek, J. N. H. Wide Bite Angle Diphosphines: Xantphos Ligands in Transition Metal Complexes and Catalysis. Acc. Chem. Res. 2001, 34, 895904,  DOI: 10.1021/ar000060+
    2. 2
      Teng, Q.; Huynh, H. V. Determining the Electron-Donating Properties of Bidentate Ligands by 13C NMR Spectroscopy. Inorg. Chem. 2014, 53, 1096410973,  DOI: 10.1021/ic501325j
    3. 3
      (a) Johnson, L. K.; Killian, C. M.; Brookhart, M. New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and α-Olefins. J. Am. Chem. Soc. 1995, 117, 64146415,  DOI: 10.1021/ja00128a054 .
      (b) Killian, C. M.; Tempel, D. J.; Johnson, L. K.; Brookhart, M. Living Polymerization of α-Olefins Using NiII–α-Diimine Catalysts. Synthesis of New Block Polymers Based on α-Olefins. J. Am. Chem. Soc. 1996, 118, 1166411665,  DOI: 10.1021/ja962516h .
      (c) Mecking, S.; Johnson, L. K.; Wang, L.; Brookhart, M. Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and α-Olefins with Methyl Acrylate. J. Am. Chem. Soc. 1998, 120, 888899,  DOI: 10.1021/ja964144i .

      For review, see:

      (d) Ittel, S. D.; Johnson, L. K.; Brookhart, M. Late-Metal Catalysts for Ethylene Homo- and Copolymerization. Chem. Rev. 2000, 100, 11691204,  DOI: 10.1021/cr9804644
    4. 4

      For recent examples, see:

      (a) Takano, S.; Takeuchi, D.; Osakada, K.; Akamatsu, N.; Shishido, A. Dipalladium Catalyst for Olefin Polymerization: Introduction of Acrylate Units into the Main Chain of Branched Polyethylene. Angew. Chem., Int. Ed. 2014, 53, 92469250,  DOI: 10.1002/anie.201404339 .
      (b) Allen, K. E.; Campos, J.; Daugulis, O.; Brookhart, M. Living Polymerization of Ethylene and Copolymerization of Ethylene/Methyl Acrylate Using “Sandwich” Diimine Palladium Catalysts. ACS Catal. 2015, 5, 456464,  DOI: 10.1021/cs5016029 .
      (c) Dai, S.; Sui, X.; Chen, C. Highly Robust Palladium(II) α-Diimine Catalysts for Slow-Chain-Walking Polymerization of Ethylene and Copolymerization with Methyl Acrylate. Angew. Chem., Int. Ed. 2015, 54, 99489953,  DOI: 10.1002/anie.201503708 .
      (d) Long, B. K.; Eagan, J. M.; Mulzer, M.; Coates, G. W. Semi-Crystalline Polar Polyethylene: Ester-Functionalized Linear Polyolefins Enabled by a Functional-Group-Tolerant, Cationic Nickel Catalyst. Angew. Chem., Int. Ed. 2016, 55, 71067110,  DOI: 10.1002/anie.201601703 .
      (e) Dai, S.; Zhou, S.; Zhang, W.; Chen, C. Systematic Investigations of Ligand Steric Effects on α-Diimine Palladium Catalyzed Olefin Polymerization and Copolymerization. Macromolecules 2016, 49, 88558862,  DOI: 10.1021/acs.macromol.6b02104 .
      (f) Dai, S.; Chen, C. Direct Synthesis of Functionalized High-Molecular-Weight Polyethylene by Copolymerization of Ethylene with Polar Monomers. Angew. Chem., Int. Ed. 2016, 55, 1328113285,  DOI: 10.1002/anie.201607152 .
      (g) Chen, Z.; Liu, W.; Daugulis, O.; Brookhart, M. Mechanistic Studies of Pd(II)-Catalyzed Copolymerization of Ethylene and Vinylalkoxysilanes: Evidence for a β-Silyl Elimination Chain Transfer Mechanism. J. Am. Chem. Soc. 2016, 138, 1612016129,  DOI: 10.1021/jacs.6b10462 .
      (h) Zhao, M.; Chen, C. Accessing Multiple Catalytically Active States in Redox-Controlled Olefin Polymerization. ACS Catal. 2017, 7, 74907494,  DOI: 10.1021/acscatal.7b02564 .
      (i) Li, M.; Wang, X.; Luo, Y.; Chen, C. A Second-Coordination-Sphere Strategy to Modulate Nickel- and Palladium-Catalyzed Olefin Polymerization and Copolymerization. Angew. Chem., Int. Ed. 2017, 56, 1160411609,  DOI: 10.1002/anie.201706249
    5. 5
      Drent, E.; van Dijk, R.; van Ginkel, R.; van Oort, B.; Pugh, R. I. Palladium Catalysed Copolymerisation of Ethene with Alkylacrylates: Polar Comonomer Built into the Linear Polymer Chain. Chem. Commun. 2002, 744745,  DOI: 10.1039/b111252j
    6. 6

      For review, see:

      (a) Berkefeld, A.; Mecking, S. Coordination Copolymerization of Polar Vinyl Monomers H2C═CHX. Angew. Chem., Int. Ed. 2008, 47, 25382542,  DOI: 10.1002/anie.200704642 .
      (b) Nakamura, A.; Ito, S.; Nozaki, K. Coordination–Insertion Copolymerization of Fundamental Polar Monomers. Chem. Rev. 2009, 109, 52155244,  DOI: 10.1021/cr900079r .
      (c) Ito, S.; Nozaki, K. Coordination–Insertion Copolymerization of Polar Vinyl Monomers by Palladium Catalysts. Chem. Rec. 2010, 10, 315325,  DOI: 10.1002/tcr.201000032 .
      (d) Nakamura, A.; Anselment, T. M. J.; Claverie, J. P.; Goodall, B.; Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W. N. M.; Nozaki, K. Ortho-Phosphinobenzenesulfonate: A Superb Ligand for Palladium-Catalyzed Coordination–Insertion Copolymerization of Polar Vinyl Monomers. Acc. Chem. Res. 2013, 46, 14381449,  DOI: 10.1021/ar300256h .
      (e) Carrow, B. P.; Nozaki, K. Transition-Metal-Catalyzed Functional Polyolefin Synthesis: Effecting Control through Chelating Ancillary Ligand Design and Mechanistic Insights. Macromolecules 2014, 47, 25412555,  DOI: 10.1021/ma500034g .
      (f) Guo, L.; Dai, S.; Sui, X.; Chen, C. Palladium and Nickel Catalyzed Chain Walking Olefin Polymerization and Copolymerization. ACS Catal. 2016, 6, 428441,  DOI: 10.1021/acscatal.5b02426
    7. 7

      For recent examples not included in ref (6d), see:

      (a) Leicht, H.; Göttker-Schnetmann, I.; Mecking, S. Incorporation of Vinyl Chloride in Insertion Polymerization. Angew. Chem., Int. Ed. 2013, 52, 39633966,  DOI: 10.1002/anie.201209724 .
      (b) Wucher, P.; Goldbach, V.; Mecking, S. Electronic Influences in Phosphinesulfonato Palladium(II) Polymerization Catalysts. Organometallics 2013, 32, 45164522,  DOI: 10.1021/om400297x .
      (c) Lanzinger, D.; Giuman, M. M.; Anselment, T. M. J.; Rieger, B. Copolymerization of Ethylene and 3,3,3-Trifluoropropene Using (Phosphine-sulfonate)Pd(Me)(DMSO) as Catalyst. ACS Macro Lett. 2014, 3, 931934,  DOI: 10.1021/mz5004344 .
      (d) Jian, Z.; Wucher, P.; Mecking, S. Heterocycle-Substituted Phosphinesulfonato Palladium(II) Complexes for Insertion Copolymerization of Methyl Acrylate. Organometallics 2014, 33, 28792888,  DOI: 10.1021/om500400a .
      (e) Ota, Y.; Ito, S.; Kuroda, J.; Okumura, Y.; Nozaki, K. Quantification of the Steric Influence of Alkylphosphine–Sulfonate Ligands on Polymerization, Leading to High-Molecular-Weight Copolymers of Ethylene and Polar Monomers. J. Am. Chem. Soc. 2014, 136, 1189811901,  DOI: 10.1021/ja505558e .
      (f) Jian, Z.; Baier, M. C.; Mecking, S. Suppression of Chain Transfer in Catalytic Acrylate Polymerization via Rapid and Selective Secondary Insertion. J. Am. Chem. Soc. 2015, 137, 28362839,  DOI: 10.1021/jacs.5b00179 .
      (g) Chen, M.; Yang, B.; Chen, C. Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes. Angew. Chem., Int. Ed. 2015, 54, 1552015524,  DOI: 10.1002/anie.201507274 .
      (h) Jian, Z.; Mecking, S. Insertion Homo- and Copolymerization of Diallyl Ether. Angew. Chem., Int. Ed. 2015, 54, 1584515849,  DOI: 10.1002/anie.201508930 .
      (i) Jian, Z.; Leicht, H.; Mecking, S. Direct Synthesis of Imidazolium-Functional Polyethylene by Insertion Copolymerization. Macromol. Rapid Commun. 2016, 37, 934938,  DOI: 10.1002/marc.201600073 .
      (j) Jian, Z.; Mecking, S. Short-Chain Branched Polar-Functionalized Linear Polyethylene via “Tandem Catalysis”. Macromolecules 2016, 49, 40574066,  DOI: 10.1021/acs.macromol.6b00581 .
      (k) Jian, Z.; Mecking, S. Insertion Polymerization of Divinyl Formal. Macromolecules 2016, 49, 43954403,  DOI: 10.1021/acs.macromol.6b00983 .
      (l) Ota, Y.; Ito, S.; Kobayashi, M.; Kitade, S.; Sakata, K.; Tayano, T.; Nozaki, K. Crystalline Isotactic Polar Polypropylene from the Palladium-Catalyzed Copolymerization of Propylene and Polar Monomers. Angew. Chem., Int. Ed. 2016, 55, 75057509,  DOI: 10.1002/anie.201600819 .
      (m) Wada, S.; Jordan, R., F. Olefin Insertion into a Pd–F Bond: Catalyst Reactivation Following β-F Elimination in Ethylene/Vinyl Fluoride Copolymerization. Angew. Chem., Int. Ed. 2017, 56, 18201824,  DOI: 10.1002/anie.201611198 .
      (n) Zhang, D.; Chen, C. Influence of Polyethylene Glycol Unit on Palladium- and Nickel-Catalyzed Ethylene Polymerization and Copolymerization. Angew. Chem., Int. Ed. 2017, 56, 1467214676,  DOI: 10.1002/anie.201708212
    8. 8
      (a) Nakano, R.; Nozaki, K. Copolymerization of Propylene and Polar Monomers Using Pd/IzQO Catalysts. J. Am. Chem. Soc. 2015, 137, 1093410937,  DOI: 10.1021/jacs.5b06948 .
      (b) Tao, W.; Nakano, R.; Ito, S.; Nozaki, K. Copolymerization of Ethylene and Polar Monomers by Using Ni/IzQO Catalysts. Angew. Chem., Int. Ed. 2016, 55, 28352839,  DOI: 10.1002/anie.201510077 .
      (c) Yasuda, H.; Nakano, R.; Ito, S.; Nozaki, K. Palladium/IzQO-Catalyzed Coordination–Insertion Copolymerization of Ethylene and 1,1-Disubstituted Ethylenes Bearing a Polar Functional Group. J. Am. Chem. Soc. 2018, 140, 18761883,  DOI: 10.1021/jacs.7b12593
    9. 9
      (a) Nagai, Y.; Kochi, T.; Nozaki, K. Synthesis of N-Heterocyclic Carbene-Sulfonate Palladium Complexes. Organometallics 2009, 28, 61316134,  DOI: 10.1021/om9004252 .
      (b) Zhou, X.; Jordan, R. F. Synthesis, cis/trans Isomerization, and Reactivity of Palladium Alkyl Complexes That Contain a Chelating N-Heterocyclic-Carbene Sulfonate Ligand. Organometallics 2011, 30, 46324642,  DOI: 10.1021/om200482a .
      (c) Gott, A. L.; Piers, W. E.; Dutton, J. L.; McDonald, R.; Parvez, M. Dimerization of Ethylene by Palladium Complexes Containing Bidentate Trifluoroborate-Functionalized Phosphine Ligands. Organometallics 2011, 30, 42364249,  DOI: 10.1021/om2004095 .
      (d) Kim, Y.; Jordan, R. F. Synthesis, Structures, and Ethylene Dimerization Reactivity of Palladium Alkyl Complexes That Contain a Chelating Phosphine–Trifluoroborate Ligand. Organometallics 2011, 30, 42504256,  DOI: 10.1021/om200472x .
      (e) Wucher, P.; Roesle, P.; Falivene, L.; Cavallo, L.; Caporaso, L.; Göttker-Schnetmann, I.; Mecking, S. Controlled Acrylate Insertion Regioselectivity in Diazaphospholidine-Sulfonato Palladium(II) Complexes. Organometallics 2012, 31, 85058515,  DOI: 10.1021/om300755j .
      (f) Contrella, N. D.; Sampson, J. R.; Jordan, R. F. Copolymerization of Ethylene and Methyl Acrylate by Cationic Palladium Catalysts That Contain Phosphine-Diethyl Phosphonate Ancillary Ligands. Organometallics 2014, 33, 35463555,  DOI: 10.1021/om5004489 .
      (g) Zhang, Y.; Cao, Y.; Leng, X.; Chen, C.; Huang, Z. Cationic Palladium(II) Complexes of Phosphine–Sulfonamide Ligands: Synthesis, Characterization, and Catalytic Ethylene Oligomerization. Organometallics 2014, 33, 37383745,  DOI: 10.1021/om5004094 .
      (h) Jian, Z.; Falivene, L.; Wucher, P.; Roesle, P.; Caporaso, L.; Cavallo, L.; Göttker-Schnetmann, I.; Mecking, S. Insights into Functional-Group-Tolerant Polymerization Catalysis with Phosphine–Sulfonamide Palladium(II) Complexes. Chem. - Eur. J. 2015, 21, 20622075,  DOI: 10.1002/chem.201404856 .
      (i) Sui, X.; Dai, S.; Chen, C. Ethylene Polymerization and Copolymerization with Polar Monomers by Cationic Phosphine Phosphonic Amide Palladium Complexes. ACS Catal. 2015, 5, 59325937,  DOI: 10.1021/acscatal.5b01490
    10. 10
      (a) Noda, S.; Nakamura, A.; Kochi, T.; Chung, L. W.; Morokuma, K.; Nozaki, K. Mechanistic Studies on the Formation of Linear Polyethylene Chain Catalyzed by Palladium Phosphine–Sulfonate Complexes: Experiment and Theoretical Studies. J. Am. Chem. Soc. 2009, 131, 1408814100,  DOI: 10.1021/ja9047398 .
      (b) Nakano, R.; Chung, L. W.; Watanabe, Y.; Okuno, Y.; Okumura, Y.; Ito, S.; Morokuma, K.; Nozaki, K. Elucidating the Key Role of Phosphine–Sulfonate Ligands in Palladium-Catalyzed Ethylene Polymerization: Effect of Ligand Structure on the Molecular Weight and Linearity of Polyethylene. ACS Catal. 2016, 6, 61016113,  DOI: 10.1021/acscatal.6b00911
    11. 11
      Wu, Z.; Chen, M.; Chen, C. Ethylene Polymerization and Copolymerization by Palladium and Nickel Catalysts Containing Naphthalene-Bridged Phosphine–Sulfonate Ligands. Organometallics 2016, 35, 14721479,  DOI: 10.1021/acs.organomet.6b00076
    12. 12
      (a) Murry, R. E. U.S. Patent 4,689,437. Aug 25, 1987.
      (b) van Doorn, J. A.; Drent, E.; van Leeuwen, P. W. M. N.; Meijboon, N.; van Oort, A. B.; Wife, R. L. Eur. Pat. Appl. 0,280,380, Aug 31, 1988.
      (c) Keim, W.; Maas, H.; Mecking, S. Palladium Catalyzed Alternating Cooligomerization of Ethylene and Carbon Monoxide to Unsaturated Ketones. Z. Naturforsch., B: J. Chem. Sci. 1995, 50, 430438,  DOI: 10.1515/znb-1995-0318 .
      (d) Bennett, J. L.; Brookhart, M.; Johnson, L. K.; PCT Int. Appl. WO199830610, July 16, 1998.
      (e) Brassat, I.; Keim, W.; Killat, S.; Möthrath, M.; Mastrorilli, P.; Nobile, C. F.; Suranna, G. P. Synthesis and Catalytic Activity of Allyl, Methallyl and Methyl Complexes of Nickel(II) and Palladium(II) with Biphosphine Monoxide Ligands: Oligomerization of Ethylene and Copolymerization of Ethylene and Carbon Monoxide. J. Mol. Catal. A: Chem. 2000, 157, 4158,  DOI: 10.1016/S1381-1169(99)00449-5 .
      (f) Malinoski, J. M.; Brookhart, M. Polymerization and Oligomerization of Ethylene by Cationic Nickel(II) and Palladium(II) Complexes Containing Bidentate Phenacyldiarylphosphine Ligands. Organometallics 2003, 22, 53245335,  DOI: 10.1021/om030388h .
      (g) Bettucci, L.; Bianchini, C.; Claver, C.; Suarez, E. J. G.; Ruiz, A.; Meli, A.; Oberhauser, W. Ligand Effects in the Non-alternating CO–Ethylene Copolymerization by Palladium(II) Catalysis. Dalton Trans. 2007, 55905602,  DOI: 10.1039/b711280g
    13. 13
      Liu, W.; Malinoski, J. M.; Brookhart, M. Ethylene Polymerization and Ethylene/Methyl 10-Undecenoate Copolymerization Using Nickel(II) and Palladium(II) Complexes Derived from a Bulky P,O Chelating Ligand. Organometallics 2002, 21, 28362838,  DOI: 10.1021/om0201516
    14. 14
      Black, R. E.; Jordan, R. F. Synthesis and Reactivity of Palladium(II) Alkyl Complexes that Contain Phosphine-cyclopentanesulfonate Ligands. Organometallics 2017, 36, 34153428,  DOI: 10.1021/acs.organomet.7b00572
    15. 15
      (a) Carrow, B. P.; Nozaki, K. Synthesis of Functional Polyolefins Using Cationic Bisphosphine Monoxide–Palladium Complexes. J. Am. Chem. Soc. 2012, 134, 88028805,  DOI: 10.1021/ja303507t .
      (b) Mitsushige, Y.; Carrow, B. P.; Ito, S.; Nozaki, K. Ligand-Controlled Insertion Regioselectivity Accelerates Copolymerisation of Ethylene with Methyl Acrylate by Cationic Bisphosphine Monoxide–Palladium Catalysts. Chem. Sci. 2016, 7, 737744,  DOI: 10.1039/C5SC03361F
    16. 16
      A part of the present work has already been disclosed in a patent, see:Nozaki, K.; Carrow, B. P.; Okumura, Y.; Kuroda, J. WO2013168626, 2013.
    17. 17
      The amount of ethylene dissolved in toluene does not linearly correlate with the pressure of ethylene, especially when the pressure of ethylene is <0.5 MPa; see:Schuster, N.; Rünzi, T.; Mecking, S. Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization. Macromolecules 2016, 49, 11721179,  DOI: 10.1021/acs.macromol.5b02749
    18. 18
      Ito, S.; Kanazawa, M.; Munakata, K.; Kuroda, J.; Okumura, Y.; Nozaki, K. Coordination–Insertion Copolymerization of Allyl Monomers with Ethylene. J. Am. Chem. Soc. 2011, 133, 12321235,  DOI: 10.1021/ja1092216
    19. 19

      For details, see Figure S63 in the Supporting Information.

    20. 20
      There are several types of ethylene/MMA copolymers formed via late transition metal catalysis: (1) ethylene/MMA copolymers featuring chain-end incorporation of MMA formed via coordination–insertion mechanism (for the recent example, see:Chen, M.; Chen, C. A Versatile Ligand Platform for Palladium- and Nickel-catalyzed Ethylene Copolymerizations with Polar Monomers. Angew. Chem., Int. Ed. 2018, in press. DOI:  DOI: 10.1002/anie.201711753 ); (2) multiblock ethylene/MMA copolymers by a combination of coordination–insertion and radical mechanisms; (3) ethylene/MMA copolymers which might include consecutive polyMMA units formed by the intermediacy of radical-related processes. For the details, see ref (8c) and references cited therein.
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsmacrolett.8b00034.

    • Experimental procedure, NMR spectra of complexes and (co)polymers, and X-ray crystallographic data (PDF).


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE