M–H–BR3 and M–Br–BR3 interactions in rhodium and nickel complexes of an ambiphilic phosphine–thioether–borane ligand
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abstract
Reaction of [Rh(μ-Cl)(CO)(TXPB)] (1; TXPB = 2,7-di-tert-butyl-5-diphenylboryl-4-diphenylphosphino-9,9-dimethylthioxanthene) with NaBH4 yielded square planar [Rh(μ-H)(CO)(TXPB)] (2) in which the hydride ligand bridges between rhodium and the borane unit of TXPB. The Rh–H, Rh–B, and Rh–Cipso distances are short at 1.84(5), 2.456(6), and 2.568(5) Å, respectively, whereas the B–H bond, 1.59(6) Å, falls at the longer end of the usual range. Compound 2 is compared with the previously reported series of rhodium TXPB complexes: [RhX(CO)(TXPB)] {X = F (3), Cl (1), Br (4), I (5)}. Compound 4 in this series features the only crystallographically characterized example of an M–Br–BR3 interaction, and to expand this area, [NiBr(μ-Br)(TXPB)] (6) was prepared via the reaction of [NiBr2(dme)2] (dme = 1,2-dimethoxyethane) with TXPB. An X-ray crystal structure of light purple 6 revealed a square-planar geometry with a strong B–Br interaction {B–Br = 2.311(6) Å; ∑(C–B–C) = 344.5(7)°}. An 11B NMR chemical shift of 23 ppm was observed for 6, indicating that an appreciable B–Br interaction is maintained in solution. No signals were observed in the 31P{1H} NMR spectrum at room temperature, whereas a broadened 31P signal was observed at −20 °C, evolving into a sharp singlet at −67 °C. This behaviour suggests that at room temperature, square planar 6 exists in equilibrium with a paramagnetic tetrahedral isomer, present at a level below that detectable through Evans magnetic measurements.
