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The reactions of group IVB hydrides with carbonyl complexes of cobalt and manganese Foster, Stephen Paul Mackay, Kenneth M. Nicholson, Brian K. The use of the hydrides as reagents for building group IVB - transition metal complexes has been investigated. The reactions of the simple hydrides; Me₃GeH, Me₂GeH₂, MeGeH₃, GeH₄, Me₂SiH₂, Me₂SnH₂, MeSnH₃, and SnH₄, with Co₂(CO)₈ have been examined, and the effect determined of, reactant ratios and amount of CO present, on the products obtained. Limited evidence was obtained for the synthesis of the new compounds; MeGe[Co(CO)₄]₃, HGe[Co(CO)₄]₃, Me₂SiHCo(CO)₄ and (OC)₄CoMe₂SiOCCo₃(CO)₉. Me₂GeH₂ replaces a bridging CO group: Me₂GeH₂ + Co₂(CO)₈ → Me₂GeCo₂(CO)₇ + H₂ + CO Me₂GeH₂ + Me₂GeCo₂(CO) ₇ → (Me₂Ge)₂Co₂(CO)₆ + H₂ + CO In the reactions of the polygermanes; Me₃GeGeH₃, Me₃SiGeH₃, Ge₂H₆, Ge₃H₈ and (GeH₃)₂SiMe₂ with Co₂(CO)₈, the M'-Ge, (M' = Si or Ge) bonds were quantitatively cleaved, and the new compound Ge₂Co₆(CO)₂₀, was isolated. This compound is assigned the structure: on spectroscopic evidence. Me₂GeH₂ also replaces a bridging CO group in the germanium - cobalt carbonyl species, to produce the new compounds; Me₂Ge₂Co₄(CO)₁₃ and (Me₂Ge)₂Ge₂Co₆(CO)₁₈. An X-ray crystallographic study on Me₂Ge₂Co₄(CO)₁₃ although showing the: skeleton, failed to refine properly. The reactions of Me₂SiH₂ and Me₂SnH₂ with germanium - cobalt carbonyl species failed to give a similar result. MeGeH₃ and GeCo₄(Co)₁₄ produced initially the analogous Me(H)Ge₂Co₄(CO)₁₃. However when left for 6 months, an unexpected rearrangement yielded (MeGe)₂Co₄(CO)₁₁. X-ray crystallography showed an irregular square bipyramidal structure, containing 5-coordinated square pyramidal germanium. This is this first example of such a group IVB - transition metal cluster. The decarbonylation of Ge₂Co₆(CO)₂₀ yielded the new compound [(OC)₄CoGe]₂Co₄(CO)₁₁ : which was found by X-ray crystallography to have a similar square bipyramidal structure. The new tin hydrides; MeSnH₂Mn(CO)₅ and Me₂SnHMn(CO)₅, have been prepared by the established route : Me₍₃₋ₓ₎SnHₓCl + NaMn(CO)₅ → Me₍₃₋ₓ₎SnHₓMn(CO)₅ + NaCl (x = 1,2) and characterised spectroscopically. The University of Waikato 1982 Thesis en https://hdl.handle.net/10289/16237 https://researchcommons.waikato.ac.nz/bitstreams/76eaaa91-89e2-4be9-a23e-ef17b85b83e7/download 5bdc1977f020a4b0930b5c005c474b43 https://researchcommons.waikato.ac.nz/bitstreams/b109eeef-d4a8-4021-921f-966a2f426818/download e14202ab27e47ddb00d33097327ba050 https://researchcommons.waikato.ac.nz/bitstreams/27c82543-ad59-42b8-9d3e-b9dbf23c4466/download 27fc56b47ea9ef15266dad350b1d134c All items in Research Commons are provided for private study and research purposes and are protected by copyright with all rights reserved unless otherwise indicated.