Iridium Pincer Catalysts for Silane Dehydrocoupling: Ligand Effects on Selectivity and Activity

Autor:	Rory Waterman, Neil T. Mucha
Rok vydání:	2015
Předmět:	Steric effects Silanes Organic Chemistry chemistry.chemical_element Photochemistry Silane Catalysis Inorganic Chemistry chemistry.chemical_compound POCOP chemistry Polymer chemistry Redistribution (chemistry) Iridium Physical and Theoretical Chemistry Selectivity
Zdroj:	Organometallics. 34:3865-3872
ISSN:	1520-6041 0276-7333
Popis:	Catalytic reactions of bisphosphinite pincer-ligated iridium compounds p-XR(POCOP)IrHCl (POCOP) [2,6-(R2PO)2C6H3, R = iPr, X = H (1); R = tBu, X = COOMe (2); = H (3); = NMe2 (4)] with primary and secondary silanes have been performed. Complex 1 is primarily a silane redistribution precatalyst, but dehydrocoupling catalysis is observed for sterically demanding silane substrates or with aggressive removal of H2. The bulkier compounds (2–4) are silane dehydrocoupling precatalysts that also undergo competitive redistribution with less hindered substrates. Products generated from reactions utilizing 2–4 include low molecular weight oligosilanes with varying degrees of redistribution present or disilanes when employing more sterically demanding silane substrates. Selectivity for redistribution versus dehydrocoupling depends on the steric and electronic environment of the metal but can also be affected by reaction conditions.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::28649f4566849f62b7c11e67961fee6c https://doi.org/10.1021/acs.organomet.5b00486 Zobrazit plný text záznamu