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Hydrosilylation and Silane Polymerization Catalyzed by Group 4 Amidometallocene Cations
Tereza Edlová,
Adrien T. Normand 
,
Hélène Cattey,
Stéphane Brandès ,
Yue Wu,
Ariana Antonangelo,
Benjamin Théron,
Quentin Bonnin,
Mariolino Carta ,
Pierre Le Gendre
,
Hélène Cattey,
Stéphane Brandès ,
Yue Wu,
Ariana Antonangelo,
Benjamin Théron,
Quentin Bonnin,
Mariolino Carta ,
Pierre Le Gendre
Organometallics, Volume: 42, Issue: 11, Pages: 1166 - 1178
Swansea University Authors:
Yue Wu, Ariana Antonangelo, Mariolino Carta
-
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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...
| Published in: | Organometallics |
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| ISSN: | 0276-7333 1520-6041 |
| Published: |
American Chemical Society (ACS)
2023
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| Online Access: |
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| 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). |
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| College: |
Faculty of Science and Engineering |
| Issue: |
11 |
| Start Page: |
1166 |
| End Page: |
1178 |