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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

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
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa62935
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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 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).
College: Faculty of Science and Engineering
Issue: 11
Start Page: 1166
End Page: 1178