Bis(diethylphosphino)methane As a Bridging Ligand in Complexes of Ir2, Rh2, and IrRh: Geminal C–H Activation of α-Olefins

Autor:	Michael J. Ferguson, Robert McDonald, D. Jason Anderson, Martin R. Cowie, Michael E. Slaney
Rok vydání:	2012
Předmět:	Aqueous solution Hydride Organic Chemistry Inorganic chemistry chemistry.chemical_element Protonation Bridging ligand Medicinal chemistry Rhodium Inorganic Chemistry chemistry.chemical_compound chemistry Iridium Physical and Theoretical Chemistry Methylene Triflic acid
Zdroj:	Organometallics. 31:2286-2301
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om201214z
Popis:	Bis(diethylphosphino)methane (depm, Et2PCH2PEt2) is used as a new bridging ligand for the syntheses of a series of diiridium, dirhodium, and iridium/rhodium complexes, starting from trans-[MM′Cl2(CO)2(depm)2] (M = M′ = Ir (1); M = M′ = Rh (11); M = Ir, M′ = Rh (19)). The reduction of all three chloro compounds in aqueous KOH under an atmosphere of CO produces the neutral tricarbonyl complexes [MM′(CO)3(depm)2] (M = M′ = Ir (2); M = M′ = Rh (12); M = Ir, M′ = Rh (20)). Protonation of these tricarbonyl complexes by triflic acid (HOTf) or Brookhart’s acid (HBArF4) yields the hydride-bridged tricarbonyl complexes [MM′(CO)3(μ-H)(depm)2][X] (M = M′ = Ir (9); M = M′ = Rh (16); M = Ir, M′ = Rh (25); X = SO3CF3 or B(3,5-(CF3)2C6H3)4). Reaction of 2 with methyl triflate yields the methylene/hydride product [Ir2(H)(CO)3(μ-CH2)(depm)2][OTf] (4), while the same reaction with the dirhodium analogue (12) produces the methyl complex [Rh2(CH3)(CO)3(depm)2][OTf] (14) at below −20 °C, which upon warming to above −20 °C resu...
Databáze:	OpenAIRE
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