Identifying the missing link in catalyst&nbsp;transfer polymerization

He, Weiying; Patrick, Brian O.; Kennepohl, Pierre

doi:10.1038/s41467-018-06324-9

Identifying the missing link in catalyst transfer polymerization

Journal Article · Mon Sep 24 00:00:00 EDT 2018 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-06324-9· OSTI ID:1624115

^[1]; Patrick, Brian O. ^[2]; ^[2]

Univ. of British Columbia, Vancouver, BC (Canada); DOE/OSTI
Univ. of British Columbia, Vancouver, BC (Canada)

Nickel-catalyzed catalyst transfer polycondensation (CTP) of thiophenes is an efficient strategy for the controlled synthesis of polythiophenes. However, a detailed view of its reaction mechanism has remained elusive with unresolved questions regarding the geometry and bonding of critical Ni(0) thiophene intermediates. Herein, we provide experimental and computational evidence of structurally characterized square planar η²-Ni(0)–thiophene species and their relevance to the mechanism of CTP. These results confirm the viability of C,C-η² bound intermediates in CTP of thiophenes, providing an electronic rationale for the stability of such species, and thus that such processes can proceed as living polymerizations. We further show that C,S-κ² species may also be relevant in nickel-catalyzed CTP of thiophenes, providing new avenues for exploitation and optimization.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); Natural Sciences and Engineering Research Council (NSERC); National Institutes of Health (NIH), National Institute of General Medical Sciences (NIGMS)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1624115

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 9; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

Charge Decomposition Analysis of the Electron Localizability Indicator: A Bridge between the Orbital and Direct Space Representation of the Chemical Bond Wagner, Frank R.; Bezugly, Viktor; Kohout, Miroslav Chemistry - A European Journal, Vol. 13, Issue 20 https://doi.org/10.1002/chem.200700013	journal	July 2007
Diversifying Cross-Coupling Strategies, Catalysts and Monomers for the Controlled Synthesis of Conjugated Polymers Baker, Matthew A.; Tsai, Chia-Hua; Noonan, Kevin J. T. Chemistry - A European Journal, Vol. 24, Issue 50 https://doi.org/10.1002/chem.201706102	journal	June 2018
The three-center-four-electron (3c-4e) bond nature revisited. An atoms-in-molecules theory (AIM) and ELF study Molina Molina, José; Dobado, José A. Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 105, Issue 4-5 https://doi.org/10.1007/s002140000231	journal	April 2001
Structural aspects of thiophene coordination in transition metal complexes Angelici, R. Coordination Chemistry Reviews, Vol. 105, Issue 1 https://doi.org/10.1016/0010-8545(90)80018-O	journal	November 1990
Matchmaking in Catalyst-Transfer Polycondensation: Optimizing Catalysts based on Mechanistic Insight Leone, Amanda K.; McNeil, Anne J. Accounts of Chemical Research, Vol. 49, Issue 12 https://doi.org/10.1021/acs.accounts.6b00488	journal	November 2016
Transformation of Step-Growth Polymerization into Living Chain-Growth Polymerization Yokozawa, Tsutomu; Ohta, Yoshihiro Chemical Reviews, Vol. 116, Issue 4 https://doi.org/10.1021/acs.chemrev.5b00393	journal	November 2015
Nickel-Catalyzed Suzuki Polycondensation for Controlled Synthesis of Ester-Functionalized Conjugated Polymers Qiu, Yunyan; Worch, Joshua C.; Fortney, Andria Macromolecules, Vol. 49, Issue 13 https://doi.org/10.1021/acs.macromol.6b01006	journal	June 2016
Advances in Molecular Design and Synthesis of Regioregular Polythiophenes Osaka, Itaru; McCullough, Richard D. Accounts of Chemical Research, Vol. 41, Issue 9 https://doi.org/10.1021/ar800130s	journal	September 2008
A quantum theory of molecular structure and its applications Bader, Richard F. W. Chemical Reviews, Vol. 91, Issue 5 https://doi.org/10.1021/cr00005a013	journal	July 1991
Structure of Thiophenechromium Tricarbonyl, C ₄ H ₄ SCr(CO) ₃ Bailey, Marcia F.; Dahl, Lawrence F. Inorganic Chemistry, Vol. 4, Issue 9 https://doi.org/10.1021/ic50031a016	journal	September 1965
(Tetramethylthiophene)ruthenium dichloride dimer: a versatile synthetic intermediate in thiophene coordination chemistry Lockemeyer, John R.; Rauchfuss, Thomas B.; Rheingold, Arnold L. Journal of the American Chemical Society, Vol. 111, Issue 24 https://doi.org/10.1021/ja00206a010	journal	November 1989
21-Thiatetra-p-tolylporphyrin and its copper(II) bicarbonate complex. Structural effects of copper-thiophene binding Latos-Grazynski, Lechoslaw; Lisowski, Jerzy; Olmstead, Marilyn M. Journal of the American Chemical Society, Vol. 109, Issue 14 https://doi.org/10.1021/ja00248a067	journal	July 1987
Random Catalyst Walking along Polymerized Poly(3-hexylthiophene) Chains in Kumada Catalyst-Transfer Polycondensation Tkachov, Roman; Senkovskyy, Volodymyr; Komber, Hartmut Journal of the American Chemical Society, Vol. 132, Issue 22 https://doi.org/10.1021/ja102210r	journal	June 2010
Competitive Carbon−Sulfur vs Carbon−Carbon Bond Activation of 2-Cyanothiophene with [Ni(dippe)H] ₂ Grochowski, Matthew R.; Li, Ting; Brennessel, William W. Journal of the American Chemical Society, Vol. 132, Issue 35 https://doi.org/10.1021/ja104158h	journal	September 2010
Dipalladium(I) Terphenyl Diphosphine Complexes as Models for Two-Site Adsorption and Activation of Organic Molecules Lin, Sibo; Herbert, David E.; Velian, Alexandra Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja406696k	journal	October 2013
Mechanistic Studies on Ni(dppe)Cl ₂ -Catalyzed Chain-Growth Polymerizations: Evidence for Rate-Determining Reductive Elimination Lanni, Erica L.; McNeil, Anne J. Journal of the American Chemical Society, Vol. 131, Issue 45 https://doi.org/10.1021/ja904197q	journal	November 2009
Room-Temperature Desulfurization of Dibenzothiophene Mediated by [( i -Pr ₂ PCH ₂ ) ₂ NiH] ₂ Vicic, David A.; Jones, William D. Journal of the American Chemical Society, Vol. 119, Issue 44 https://doi.org/10.1021/ja972544f	journal	November 1997
Modeling the Hydrodesulfurization Reaction at Nickel. Unusual Reactivity of Dibenzothiophenes Relative to Thiophene and Benzothiophene Vicic, David A.; Jones, William D. Journal of the American Chemical Society, Vol. 121, Issue 33 https://doi.org/10.1021/ja9905997	journal	August 1999
Synthesis of 2-Nickela(II)oxetanes from Nickel(0) and Epoxides: Structure, Reactivity, and a New Mechanism of Formation Desnoyer, Addison N.; Bowes, Eric G.; Patrick, Brian O. Journal of the American Chemical Society, Vol. 137, Issue 40 https://doi.org/10.1021/jacs.5b06735	journal	September 2015
Chain-Growth Polymerization for Poly(3-hexylthiophene) with a Defined Molecular Weight and a Low Polydispersity Yokoyama, Akihiro; Miyakoshi, Ryo; Yokozawa, Tsutomu Macromolecules, Vol. 37, Issue 4 https://doi.org/10.1021/ma035396o	journal	February 2004
Chain Growth Mechanism for Regioregular Nickel-Initiated Cross-Coupling Polymerizations Sheina, Elena E.; Liu, Jinsong; Iovu, Mihaela Corina Macromolecules, Vol. 37, Issue 10 https://doi.org/10.1021/ma0357063	journal	May 2004
Experimental Evidence for the Quasi-“Living” Nature of the Grignard Metathesis Method for the Synthesis of Regioregular Poly(3-alkylthiophenes) Iovu, Mihaela Corina; Sheina, Elena E.; Gil, Roberto R. Macromolecules, Vol. 38, Issue 21 https://doi.org/10.1021/ma051122k	journal	October 2005
Evidence for Ligand-Dependent Mechanistic Changes in Nickel-Catalyzed Chain-Growth Polymerizations Lanni, Erica L.; McNeil, Anne J. Macromolecules, Vol. 43, Issue 19 https://doi.org/10.1021/ma101565u	journal	October 2010
Controlled Chain-Growth Kumada Catalyst Transfer Polycondensation of a Conjugated Alternating Copolymer Ono, Robert J.; Kang, Songsu; Bielawski, Christopher W. Macromolecules, Vol. 45, Issue 5 https://doi.org/10.1021/ma300013e	journal	February 2012
Evidence for Catalyst Association in the Catalyst Transfer Polymerization of Thieno[3,2- b ]thiophene Willot, Pieter; Koeckelberghs, Guy Macromolecules, Vol. 47, Issue 24 https://doi.org/10.1021/ma502139n	journal	December 2014
On the Role of Disproportionation Energy in Kumada Catalyst-Transfer Polycondensation Bilbrey, Jenna A.; Sontag, S. Kyle; Huddleston, N. Eric ACS Macro Letters, Vol. 1, Issue 8 https://doi.org/10.1021/mz3002929	journal	July 2012
Sulfur-coordinated thiophene and dibenzothiophene in Cp'(CO)2Re(thiophene) complexes Choi, Moon Gun.; Angelici, Robert J. Organometallics, Vol. 10, Issue 7 https://doi.org/10.1021/om00053a056	journal	July 1991
A model for thiophene chemisorption: a stabilized, .eta.1S-thiophene complex and its relationship to .eta.5-coordination Draganjac, M.; Ruffing, Charles J.; Rauchfuss, Thomas B. Organometallics, Vol. 4, Issue 10 https://doi.org/10.1021/om00129a045	journal	October 1985
Thiophenes in Organotransition Metal Chemistry: Patterns of Reactivity Angelici, Robert J. Organometallics, Vol. 20, Issue 7 https://doi.org/10.1021/om010040r	journal	April 2001
Tungsten(0) η ² ^{-Thiophene Complexes: Dearomatization of Thiophene and Its Facile Oxidation, Protonation, and Hydrogenation} Delafuente, David A.; Myers, William H.; Sabat, Michal Organometallics, Vol. 24, Issue 8 https://doi.org/10.1021/om050050i	journal	April 2005
Electronic Structure of Xenon Difluoride Bilham, J.; Linnett, J. W. Nature, Vol. 201, Issue 4926 https://doi.org/10.1038/2011323a0	journal	March 1964
Cheap and cheerful circuits Voss, David Nature, Vol. 407, Issue 6803, p. 442-444 https://doi.org/10.1038/35035212	journal	September 2000
Bottom-up organic integrated circuits Smits, Edsger C. P.; Mathijssen, Simon G. J.; van Hal, Paul A. Nature, Vol. 455, Issue 7215 https://doi.org/10.1038/nature07320	journal	October 2008
Design strategies for organic semiconductors beyond the molecular formula Henson, Zachary B.; Müllen, Klaus; Bazan, Guillermo C. Nature Chemistry, Vol. 4, Issue 9 https://doi.org/10.1038/nchem.1422	journal	August 2012
Using push to get pull Groves, John T. Nature Chemistry, Vol. 6, Issue 2 https://doi.org/10.1038/nchem.1855	journal	January 2014
Solution-based electrical doping of semiconducting polymer films over a limited depth Kolesov, Vladimir A.; Fuentes-Hernandez, Canek; Chou, Wen-Fang Nature Materials, Vol. 16, Issue 4 https://doi.org/10.1038/nmat4818	journal	December 2016
High thermal conductivity of chain-oriented amorphous polythiophene Singh, Virendra; Bougher, Thomas L.; Weathers, Annie Nature Nanotechnology, Vol. 9, Issue 5 https://doi.org/10.1038/nnano.2014.44	journal	March 2014
Polymer solar cells with enhanced open-circuit voltage and efficiency Chen, Hsiang-Yu; Hou, Jianhui; Zhang, Shaoqing Nature Photonics, Vol. 3, Issue 11, p. 649-653 https://doi.org/10.1038/nphoton.2009.192	journal	November 2009
Transition-metal mediated carbon–sulfur bond activation and transformations Wang, Liandi; He, Wei; Yu, Zhengkun Chem. Soc. Rev., Vol. 42, Issue 2 https://doi.org/10.1039/C2CS35323G	journal	January 2013
Catalyst-dependent intrinsic ring-walking behavior on π-face of conjugated polymers Mikami, Koichiro; Nojima, Masataka; Masumoto, Yui Polymer Chemistry, Vol. 8, Issue 10 https://doi.org/10.1039/C6PY01934J	journal	January 2017
Synthesis, reactivity, and structures of cationic ? 6-arene carbonyl complexes of rhenium(I). Crystal and molecular structures of the two isoelectronic 1,3,5-trimethylbenzene tricarbonyl complexes of rhenium(I) and tungsten(0) Calderazzo, Fausto; Poli, Rinaldo; Barbati, Aldo Journal of the Chemical Society, Dalton Transactions, Issue 6 https://doi.org/10.1039/dt9840001059	journal	January 1984

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A robust nickel catalyst with an unsymmetrical propyl-bridged diphosphine ligand for catalyst-transfer polymerization Baker, Matthew A.; Ayuso-Carrillo, Josué; Koos, Martin R. M. Polymer Journal, Vol. 52, Issue 1 https://doi.org/10.1038/s41428-019-0259-3	journal	September 2019
Catalyst-transfer polymerization of arylamines by the Buchwald–Hartwig cross-coupling Grisorio, Roberto; Suranna, Gian Paolo Polymer Chemistry, Vol. 10, Issue 15 https://doi.org/10.1039/c8py01646a	journal	January 2019
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