Transition metal-mediated donor-acceptor coordination of low-oxidation state Group 14 element halides

Article abstract of DOI:10.1039/c5dt03018h

The reactivity of tungsten carbonyl adducts of Group 14 element (Ge, Sn and Pb) dihalides towards the metal-based donors (η⁵-C₅H₅)Rh(PMe₂Ph)₂ and Pt(PCy₃)₂ was examined. When (η⁵-C₅H₅)Rh(PMe₂Ph)₂ was treated with the Lewis acid supported Ge(ii) complex, THF·GeCl₂·W(CO)₅, cyclopentadienyl ring activation occurred, whereas the analogous Lewis acidic units SnCl₂·W(CO)₅ and PbCl₂ form direct adducts with the Rh complex to yield Rh-Sn and Rh-Pb dative bonds. Attempts to prepare metal coordinated element(ii) hydrides by adding hydride sources to the above mentioned rhodium-E(ii) halide complexes were unsuccessful; in each case insoluble products were formed along with regeneration of free (η⁵-C₅H₅)Rh(PMe₂Ph)₂. In a parallel study, ECl₂·W(CO)₅ (E = Ge or Sn) groups were shown to participate in E-Cl oxidation addition chemistry with (Cy₃P)₂Pt to give the formal Pt(ii) complexes ClPt(PCy₃)₂ECl·W(CO)₅.