Formation and Site-Selective Reactivity of a Nonsymmetric Dinuclear Iridium BisMETAMORPhos Complex

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• 作者：Sander Oldenhof ; Frederic G. Terrade ; Martin Lutz ; Jarl Ivar van der Vlugt ; Joost N. H. Reek
• 刊名：Organometallics
• 出版年：2015
• 出版时间：July 13, 2015
• 年：2015
• 卷：34
• 期：13
• 页码：3209-3215
• 全文大小：418K
• ISSN：1520-6041

文摘

A flexible di(sulfonamidophosphine) ligand (1^H2, Ph₂PN^HS(O)₂N^HPPh₂) was synthesized from commercially available sulfamide and chlorodiphenylphosphine. Coordination of this new bisMETAMORPhos 1^H2 with [Ir(Cp*)Cl(渭-Cl)]₂ instantly led to the formation of the P,P-coordinated bimetallic complex 2 [Ir(Cp*)Cl(魏¹-P₁; 魏¹-P₂-1^H2)Ir(Cp*)Cl]. Reaction of 2 using excess NaOAc led to the formation of nonsymmetric homodinuclear complex 3 [Ir(Cp*)Cl(魏²-P,O; 魏³-P,N,C; 渭-1)Ir(Cp*)], which contains two distinctly different Ir^III centers, with a fac-P,N,C and a fac-P,O,Cl coordination environment. The ligand is overall trisanionic due to additional intramolecular C鈥揌 activation of a flanking phenyl ring. Complex 3 reacts selectively at the Ir(P,O,Cl) center with a single equivalent of HCl or H₂ to generate complexes 4 and 5, respectively. These complexes are generated via heterolytic cleavage of the H鈥揅l or H鈥揌 bond, which reprotonates the ligand showing its bifunctional applicability. The Ir鈥揅 bond is found to be inert under these conditions.