Formation and Site-Selective Reactivity of a Nonsymmetric Dinuclear Iridium BisMETAMORPhos Complex
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https://figshare.com/articles/dataset/Formation_and_Site_Selective_Reactivity_of_a_Nonsymmetric_Dinuclear_Iridium_BisMETAMORPhos_Complex/2150857
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资源简介：
A flexible
di(sulfonamidophosphine) ligand (1H2, Ph2PNHS(O)2NHPPh2) was synthesized from commercially available
sulfamide and chlorodiphenylphosphine. Coordination of this new bisMETAMORPhos 1H2 with [Ir(Cp*)Cl(μ-Cl)]2 instantly led to the formation of the P,P-coordinated bimetallic
complex 2 [Ir(Cp*)Cl(κ1-P1; κ1-P2-1H2)Ir(Cp*)Cl]. Reaction of 2 using excess NaOAc led to the formation of nonsymmetric
homodinuclear complex 3 [Ir(Cp*)Cl(κ2-P,O; κ3-P,N,C; μ-1)Ir(Cp*)], which contains two distinctly different IrIII 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–H 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–Cl or H–H bond, which reprotonates the ligand
showing its bifunctional applicability. The Ir–C bond is found
to be inert under these conditions.
创建时间：
2016-02-13
