Hydride Transfer from Rhodium Complexes to Triethylborane

Autor:	Daniel L. DuBois, Calvin J. Curtis, John C. Linehan, Mary Rakowski DuBois, Alex Miedaner, James A. Franz, Daniel M. Blake
Rok vydání:	2006
Předmět:	Hydrogen Hydride Organic Chemistry Triethylborane chemistry.chemical_element Photochemistry Oxidative addition Medicinal chemistry Lithium diisopropylamide Rhodium Inorganic Chemistry chemistry.chemical_compound Deprotonation chemistry Chelation Physical and Theoretical Chemistry
Zdroj:	Organometallics. 25:4414-4419
ISSN:	1520-6041 0276-7333
Popis:	The hydrides HRh(depe)2 and HRh(dmpe)2 (depe = Et2PCH2CH2PEt2, dmpe = Me2PCH2CH2PMe2) have thermodynamic hydride donor abilities comparable to LiHBEt3, as indicated by their ability to transfer a hydride ligand to Et3B to sequentially form [Et3BHBEt3]- and [HBEt3]-. HRh(depe)2 and HRh(dmpe)2 can be generated from [Rh(dmpe)2](CF3SO3) and [Rh(depe)2](CF3SO3) and hydrogen gas in the presence of a strong base such as potassium tert-butoxide or lithium diisopropylamide. This reaction proceeds through the oxidative addition of hydrogen to form the [H2Rh(diphosphine)2](CF3SO3) complexes, followed by deprotonation. The oxidative addition of H2 is favored by diphosphine ligands with electron-donating substituents and large chelate bites. In the present study, the driving force for oxidative addition of H2 follows the order [Rh(dmpe)2](CF3SO3) > [Rh(depe)2](CF3SO3) > [Rh(dppe)2](CF3SO3) with [Rh(dmpe)2](CF3SO3) binding H2 more strongly than [Rh(dppe)2](CF3SO3) (dppe = Ph2PCH2CH2PPh2) by at least 2.7 kcal/mol. The e...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::a95ba7908cc6808db1001344cea3b22c https://doi.org/10.1021/om060584z Zobrazit plný text záznamu