No abstract

[IrCl(diphosphine)]2 {diphosphine = BINAP (1a) and BPBP (1b)} were obtained as extremely air- and moisture-sensitive crystals. The structure of 1a has been determined by X-ray analysis. Complex 1a reacted easily with two equivalents of triphenylphosphine to give IrCl(binap)(PPh3) 2a quantitatively. Complexes 1a and 1b can activate RO–H groups easily and catalyze transfer hydrogenation of alkynes in methanol. On the contrary 2a does not react with methanol even at 55 °C.

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Reaction of [IrCl((S)-binap)(PPh3)] ((S)-3) with methanol gave one of the diastereomers of the cis,mer-dihydride, cis,mer-OC-6-44-A-[IrCl(H2)((S)-binap)(PPh3)] ((S)-4a) stereoselectively, the structure of which was determined crystallographically, whereas the reaction of (S)-3 with H2 produced a 1:1 mixture of the diastereomers of the cis,mer-dihydride, (S)-4a and cis,mer-OC-6-44-C-[IrCl(H2)((S)-binap)(PPh3)] ((S)-4b).

The title complex, [Ir2(μ-Cl)2(C8H14)4], has a dinuclear structure with bridging Cl atoms, a hinge angle of 179.44 (7)° between the two IrCl2 planes, and an Ir⋯Ir distance of 3.7254 (3) Å. Regarding the coordinating C=C bonds as occupying a single coordination site each, the geometry around each Ir atom is square-planar.