The new polyhydrides [ReH5(PPh(3))(2)(L)] (1; L = 4-carbomethoxypyridine (a), pyridine (b), 4-picoline (c), 4-(dimethylamino)pyridine (d)), formed by reaction of L with [ReH7(PPh(3))(2)], are rigid on the NMR time scale at low temperature. The low-temperature spectrum is assigned by ROESY NMR studies, and turnstile and pseudorotation fluxionality mechanisms are suggested to account for the two successive coalescence events in the VT NMR spectra.
Activation of mono- and di-nuclear polyhydrides of rhenium: protonation, solvation, and oxidation
作者:Joe D. Allison、Richard A. Walton
DOI:10.1039/c39830000401
日期:——
Activation of the rheniumpolyhydrides ReH5(PPh3)2L(L = monodentate ligand) and Re2H8(PPh3)4 has been achieved through their protonation (using HBF4), the formation of solvento-complexes, and their oxidation to reactive paramagnetic cations, strategies which have led to a range of novel species, including [ReH(NCMe)3(PPh3)2L]2+, and [Re2H5(PPh3)4(CNBut)2]+ together with their ‘17-electron’ paramagnetic