Intramolecular B-H bond activation from a dihydridobis(dimethylpyrazolyl)borate ligand: Formation of a rhodium(III) carbene hydride and a rare example of reverse alpha-hydride migration
Js. Yeston et Rg. Bergman, Intramolecular B-H bond activation from a dihydridobis(dimethylpyrazolyl)borate ligand: Formation of a rhodium(III) carbene hydride and a rare example of reverse alpha-hydride migration, ORGANOMETAL, 19(16), 2000, pp. 2947-2949
The new complex Bp(2)(Me)Rh(CO)(pyridine) (1) has been prepared and reacts
with CH3I to yield the novel Rh carbene hydride complex HB(Me(2)pz)(2)Rh(H)
-(I)(C5H5N)(C(O)ME) (3), resulting from formal addition of CH3I across the
Rh-C bond concomitant with hydride transfer from B to Rh. Thermolysis of 3
induces migration of the Rh hydride to the ct-carbon to give HB(Me(2)pz)(2)
Rh(I)(C5H5N)(CH(O)Me) (6), and a crossover study, supports intramolecular m
echanisms for both hydride transfer steps.