Multiple coupling of silanes with imido complexes of Mo†
Abstract
The bis(imido) complexes (tBuN)2Mo(PMe3)(L) (L = PMe3, C2H4) react with up to three equivalents of silane PhSiH3 to give the imido-bridged disilyl silyl Mo(VI) complex (tBuN){μ-tBuN(SiHPh)2}Mo(H)(SiH2Ph)(PMe3)2 (3) studied by NMR, IR and X-ray diffraction. NMR data supported by DFT calculations show that complex 3 is an unusual example of a silyl hydride of Mo(VI), without significant Si⋯H interaction. Mechanistic NMR studies revealed that silane addition proceeds in a stepwise manner via a series of Si–H⋯M agostic and silanimine complexes whose structures were further elucidated by DFT calculations.