148722-06-9Relevant academic research and scientific papers
Reactions of the Co-ordinatively Unsaturated Cluster with Alkynes RCCR (R = Ph, C6H4Me, Me or CF3); Crystal Structures of 3-η2()-RC2R)(Ph2PCH2PPh2)> (R = Me or CF3) and Electrochemical Behaviour of Triosmium-Alkyne Clusters
Brown, Michael P.,Dolby, P. Ann,Harding, Marjorie M.,Mathews, A. Jane,Smith, Anthony K.,et al.
, p. 827 - 834 (1993)
Treatment of the unsaturated triosmium cluster 1 with diphenylacetylene leads to the formation of 2a in which the alkyne is bonded in a μ3-η2 () mode.Addition of CO to 2a gives 3a (R = Ph) in which the alkyne is bonded in a μ3-η2 () mode.Two-electron electrochemical reduction of 2a also causes this change in co-ordination mode of the alkyne ligand.Protonation of the electrochemically produced dianion 3-η2()PhC2Ph)(Ph2PCH2h2)>(2-) gives 3-η2()PhC2Ph)(PhPCH2PPh2)> 4.Th e same product 4 has also been obtained by direct hydrogenation of 2a.A similar chemical and electrochemical behaviour is observed for the ditolylacetylene derivative 2b, where the two p-methyl substituents are diagnostic in 1H NMR spectroscopy.With the alkynes RCCR (R = Me or CF3), analogous complexes to 2 are not observed, instead complexes 3-η2()-RR)(Ph2PCH2PPh2)> 3c (R = Me) and 3d (R = CF3) are obtained.Single-crystal X-ray structure determinations of 3c and 3d have been performed.
