Relative hemilabilities of H₂B(az)₂ (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C₃H₅)(CO)₂{H₂B(az)₂}] (M = Mo, W)

Abstract

The reactions of [M(η3 -C3H5)Br(CO)2(NCMe)2] (M = Mo, W) or [Mo(η3 -C3H5)Br(CO)2(PMe2Ph)2] with Na [H2B(mt)2] (mt = methimazolyl) affords the complexes [M(η3 -C3H5)(CO)2{κ3 -H,S,S’-H2B(mt)2}], the 3-centre, 2-electron B–H–M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with PMe2Ph) resulted in cleavage of the entire allyl and borate ligands to form [Mo(CO)3(PMe2Ph)3]. In contrast, the reaction of [Mo(η3 -C3H5)Br(CO)2(NCMe)2] with Na[H2B(pz)2] affords either [Mo(η3 -C3H5)(CO)2{κ3 -H,N,N’-H2B(pz)2}] or (more likely) [Mo(η3 -C3H5)(CO)2(NCMe){κ2 -N,N’-H2B(pz)2}] which in turn reacts with phosphines to provide [[Mo(η3 -C3H5)(CO)2(PPhR2){κ2 -N,N’-H2B(pz)2}] (R = Me, Ph). The reactions discussed indicate the propensity for 3-centre, 2-electron B–H–Mo interactions increases in the order H2B(pz)2 < H2B(pz*)2 < H2B(mt)2 (pz* = 3,5-dimethypyrazolyl). Show more