Amrendra K. Singh

A 4-coordinate Ru(II) imido: unusual geometry, synthesis, and reactivity

A 4-coordinate Ru(II) imido complex, Ru(NAr)(PMe3)3 (1), can be prepared from cis-RuCl2(PMe3)4 and LiNHAr. The structure of the imido is perhaps best described as a flat-based trigonal pyramid with the imido in the equatorial plane. A possible explanation for the unusual geometry is discussed, along with some reactivity of 1.

Diastereomeric control of enantioselectivity: evidence for metal cluster catalysis

Enantioselective hydrogenation of tiglic acid effected by diastereomers of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P-P*)] (P-P* = chiral Walphos diphosphine ligand) strongly supports catalysis by intact Ru3 clusters. A catalytic mechanism involving Ru3 clusters has been established by DFT calculations.

[μ-Bis(diphenyl-phosphan-yl-κP)methane]-deca-carbonyl-tri-μ-hydrido-trirhenium(I)(3 Re-Re) dichloromethane solvate.

In the title compound, [Re3(μ-H)3(C25H22P2)(CO)10]·CH2Cl2, the three Re atoms form a triangle bearing ten terminal carbonyl groups and three edge-bridging hydrides. The bis(diphenylphosphanyl)methane ligand bridges two Re atoms. Neglecting the Re—Re interactions, each Re atom is in a slightly distorted octahedral coordination environment. The dichloromethane solvent molecule is disordered over two sets of sites with fixed occupancies of 0.6 and 0.4.