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Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations

Tereza Edlová, Adrien T. Normand Orcid Logo, Hélène Cattey, Stéphane Brandès Orcid Logo, Yue Wu, Ariana Antonangelo, Benjamin Théron, Quentin Bonnin, Mariolino Carta Orcid Logo, Pierre Le Gendre Orcid Logo

Organometallics, Volume: 42, Issue: 11, Pages: 1166 - 1178

Swansea University Authors: Yue Wu, Ariana Antonangelo, Mariolino Carta Orcid Logo

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DOI (Published version): 10.1021/acs.organomet.2c00642

Abstract

Four cationic amidotitanocene complexes [Cp2Ti(NRR′)][B(C6F5)4] (Cp = η5-C5H5; 1a: R = R′ = p-anisyl; 1b: R = p-fluorophenyl, R′ = p-anisyl; 1c: R = p-fluorophenyl, R′ = phenyl; 1d: R = phenyl, R′ = 2-pyridyl) were synthesized. Complexes 1a–d undergo Ti–N bond homolysis under visible light irradiati...

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Published in: Organometallics
ISSN: 0276-7333 1520-6041
Published: American Chemical Society (ACS) 2023
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URI: https://cronfa.swan.ac.uk/Record/cronfa62935
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spelling v2 62935 2023-03-15 Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations 5c0963b4ec6334e3d4d3ca12ce7343bc Yue Wu Yue Wu true false 4565af0854d884b5f995af8f5dc652fc Ariana Antonangelo Ariana Antonangelo true false 56aebf2bba457f395149bbecbfa6d3eb 0000-0003-0718-6971 Mariolino Carta Mariolino Carta true false 2023-03-15 Four cationic amidotitanocene complexes [Cp2Ti(NRR′)][B(C6F5)4] (Cp = η5-C5H5; 1a: R = R′ = p-anisyl; 1b: R = p-fluorophenyl, R′ = p-anisyl; 1c: R = p-fluorophenyl, R′ = phenyl; 1d: R = phenyl, R′ = 2-pyridyl) were synthesized. Complexes 1a–d undergo Ti–N bond homolysis under visible light irradiation. Complexes 1a–c catalyze the polymerization of phenylsilane to yield branched polysilane polymers with molecular weights (Mw) up to approximately 3000 and dispersity indexes (Đ) of 1.4–1.6. Previously reported Group 4 cationic amidometallocene complexes [Cp2Ti(NPh2)][B(C6F5)4] (Ia) and Cp2Zr(NPh2)][MeB(C6F5)3] (IIa) were also tested in the hydrosilylation of carbonyl compounds with triethylsilane (Et3SiH). In some cases, complex Ia afforded completely reduced products (e.g., ethylbenzene from acetophenone), while IIa was generally more selective (e.g., (1-phenylethoxy)triethylsilane from acetophenone) but also more active. Complex IIa could also convert anisole derivatives to phenoxysilanes with high efficiency (TON = 2000). Journal Article Organometallics 42 11 1166 1178 American Chemical Society (ACS) 0276-7333 1520-6041 12 6 2023 2023-06-12 10.1021/acs.organomet.2c00642 COLLEGE NANME COLLEGE CODE Swansea University 2024-07-29T13:49:25.6550863 2023-03-15T10:25:55.2869451 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Tereza Edlová 1 Adrien T. Normand 0000-0002-8047-9386 2 Hélène Cattey 3 Stéphane Brandès 0000-0001-6923-1630 4 Yue Wu 5 Ariana Antonangelo 6 Benjamin Théron 7 Quentin Bonnin 8 Mariolino Carta 0000-0003-0718-6971 9 Pierre Le Gendre 0000-0003-2635-5216 10 62935__26872__62d52b40b6a843c79e18b1df06406d7a.pdf 62935.pdf 2023-03-15T10:31:17.9780220 Output 2541413 application/pdf Accepted Manuscript true 2024-03-02T00:00:00.0000000 false eng
title Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
spellingShingle Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
Yue Wu
Ariana Antonangelo
Mariolino Carta
title_short Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
title_full Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
title_fullStr Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
title_full_unstemmed Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
title_sort Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
author_id_str_mv 5c0963b4ec6334e3d4d3ca12ce7343bc
4565af0854d884b5f995af8f5dc652fc
56aebf2bba457f395149bbecbfa6d3eb
author_id_fullname_str_mv 5c0963b4ec6334e3d4d3ca12ce7343bc_***_Yue Wu
4565af0854d884b5f995af8f5dc652fc_***_Ariana Antonangelo
56aebf2bba457f395149bbecbfa6d3eb_***_Mariolino Carta
author Yue Wu
Ariana Antonangelo
Mariolino Carta
author2 Tereza Edlová
Adrien T. Normand
Hélène Cattey
Stéphane Brandès
Yue Wu
Ariana Antonangelo
Benjamin Théron
Quentin Bonnin
Mariolino Carta
Pierre Le Gendre
format Journal article
container_title Organometallics
container_volume 42
container_issue 11
container_start_page 1166
publishDate 2023
institution Swansea University
issn 0276-7333
1520-6041
doi_str_mv 10.1021/acs.organomet.2c00642
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description Four cationic amidotitanocene complexes [Cp2Ti(NRR′)][B(C6F5)4] (Cp = η5-C5H5; 1a: R = R′ = p-anisyl; 1b: R = p-fluorophenyl, R′ = p-anisyl; 1c: R = p-fluorophenyl, R′ = phenyl; 1d: R = phenyl, R′ = 2-pyridyl) were synthesized. Complexes 1a–d undergo Ti–N bond homolysis under visible light irradiation. Complexes 1a–c catalyze the polymerization of phenylsilane to yield branched polysilane polymers with molecular weights (Mw) up to approximately 3000 and dispersity indexes (Đ) of 1.4–1.6. Previously reported Group 4 cationic amidometallocene complexes [Cp2Ti(NPh2)][B(C6F5)4] (Ia) and Cp2Zr(NPh2)][MeB(C6F5)3] (IIa) were also tested in the hydrosilylation of carbonyl compounds with triethylsilane (Et3SiH). In some cases, complex Ia afforded completely reduced products (e.g., ethylbenzene from acetophenone), while IIa was generally more selective (e.g., (1-phenylethoxy)triethylsilane from acetophenone) but also more active. Complex IIa could also convert anisole derivatives to phenoxysilanes with high efficiency (TON = 2000).
published_date 2023-06-12T13:49:26Z
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score 11.028886

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