100701-36-8Relevant academic research and scientific papers
Diazoalkane activation by iridium phosphine compounds. 1. Complexes containing the intact dibenzoyldiazomethane ligand and interconversion between the η1-N-bound and a chelated N,O-bound form of the ligand accompanied by hydride migration
Cowie, Martin,Loeb, Stephen J.,McKeer, Ian R.
, p. 854 - 860 (2008/10/08)
The reaction of dibenzoyldiazomethane (N2C(C(O)Ph)2) with trans-[IrCl(N2)(PPh3)2] yields the four-coordinate species [IrCl(N2C(C(O)Ph)2)(PPh3)2] (1) in which the intact diazoalkane molecule is coordinated in a η1, singly bent geometry. Compound 1 reacts with donor ligands, L, to give five-coordinate adducts of formulation [IrCl(N2C(C(O)Ph)2)(L)(PPh3)2] (L = PMe2Ph, t-BuNC, and NO+). The reaction of 1 with 1 equiv of HCl yields an equilibrium mixture of [IrHCl2(N2C(C(O)Ph)2)(PPh3) 2] and [IrCl2(HN2C(C-(O)Ph)2)(PPh3) 2] in which hydride migration from Ir to the coordinated nitrogen atom occurs; the latter species is present in an approximate 15:1 excess. An X-ray structure determination of the second (more abundant) species was undertaken. It crystallizes in the space group P21/c with a = 10.165 (2) A?, b = 17.422 (2) A?, c = 25.653 (5) A?, β = 93.66 (2)°, V = 4533.7 A?3, and Z = 4. The structure has refined to R = 0.044 and Rw = 0.050 based on 190 variables and 1869 unique observations. The compound is a six-coordinate Ir(III) species in which the reduced diazoalkane ligand is coordinated to Ir through the terminal nitrogen atom, which also is bound to the H atom, and a benzoyl oxygen atom.
