Oxidative-addition of germanium hydrogen bonds to triosmium centers: Reactions of Os3(CO)10(μ-dPPm) and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6F14)(μ-H) with Ph3GeH

Reactions of the triosmium clusters Os-3(CO)(10)(mu-dppm) [dppm=bis(diphenylphosphino)methane] and Os-3(CO)(8)(mu(3)-Ph2PCH2P(Ph)C6H4)(mu-H) with Ph3GeH are described. With Os-3(CO)(10)(mu-dppm) at 110 degrees C the oxidative-addition product Os-3(CO)(9)(GePh3)(mu-dppm)(mu-H) (1) initially results, but further decarbonylates upon prolonged heating to give 46-electron Os-3(CO)(7)(GePh3)(mu(3)-h(2)PCH(2)P(Ph)C6H4)(mu-H)(2) (2) resulting from C-H bond activation of the diphosphine. The pre-activated Os-3(CO)(8)(mu(3)- Ph2PCH2P(Ph)C6H4)(mu-H) reacts with Ph3GeH under milder conditions (40 degrees C) to afford Os-3(CO)(8)(GePh3)(2)(mu-dppm)(mu-H)(2) (3) together with 1. Cluster 3 converts into 2 upon heating and the direct reaction between Os-3(CO)(8)(mu(3)-Ph2PCH2P(Ph)C6H4)(mu-H) and Ph3GeH at 110 degrees C also produces 2. All these clusters have been structurally characterized by single crystal X-ray diffraction analysis. (C) 2015 Elsevier B.V. All rights reserved.