87318-52-3Relevant academic research and scientific papers
Simultaneous conversion of Ni-PR3 and B-H to Ni-H and B-PR3 linkages by thermal rearrangement of d8 closo-bis(triarylphosphine)nickelacarboranes. Crystal and molecular structure of [closo-3-(μ-CO)-8-PPh3-3,1,2-NiC2B9H 10]2: A dimeric nickelacarborane complex containing a metal-metal bond
King III,Miller, Steven B.,Knobler, Carolyn B.,Hawthorne, M. Frederick
, p. 3548 - 3554 (2008/10/08)
The reaction of L2NiCl2 (L = PR3) species with nido-7,8-, nido-7,9-, or nido-2,9-C2B9H112- ions led to the formation of the corresponding icosahedral bis(phosphine)nickelacarboranes in high yield. Heating members of the closo-3,3-(triarylphosphine)2-3,1,2-NiC2B 9H11 series at 80°C in benzene solution led to the formation of the corresponding [closo-3,8-(triarylphosphine)2-3-H-3,1,2-NiC2B 9H11] by interchange of phosphine and hydrido ligands. No intermediates were observed, and the reaction was specific for the bis(triarylphosphine)-3,1,2-NiC2 icosahedral system among those investigated. The dimeric nickelacarborane carbonyl [closo-(3-(μ-CO)-8-PPh3-3,1,2-NiC2B9H 11)2] was prepared by a variety of routes such as the reaction of [closo-3,3-(PPh3)2-3,1,2-NiC2B 9H11] (1a) with CO in benzene at 80°C. A variety of ligand substitution reactions were carried out with 1a. The mechanism of the phosphine-hydride ligand interchange is discussed. The dimeric nickelacarborane complex was characterized by an X-ray diffraction study. Amber crystals were triclinic, space group P1, with a = 13.319 (4) A?, b = 10.039 (3) A?, c = 9.813 (3) A?, α = 80.00 (1)°, β = 82.91 (1)°, γ = 110.32 (1)°, and Z = 1. The structure was solved by conventional heavy-atom methods to a final discrepancy index of R = 0.057 for 2233 independent observed reflections. The complex contains a metal-metal bond (2.477 (2) A?) and two metal-bridging carbon monoxide groups.
