Organo-silyl and -germyl complexes of platinum. Part II
- 1 January 1968
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 826-834
- https://doi.org/10.1039/j19680000826
Abstract
The reactions of trans-(Et3P)2Pt(X)MMe3(M = Si, Ge and X = Cl, Ph, GePh3) with HCl in ether and in benzene are described. A high degree of selectivity is observed and the reaction when M = Ge and X = GePh3 provides a good synthetic route to trans-(Et3P)2Pt(Cl)GePh3. The reversibility of the reaction of (Et3P)2Pt(Cl)GeMe3 with hydrogen has been demonstrated and provides evidence for a hexaco-ordinate intermediate. The reactions of trans-(Et3P)2Pt(X)MMe3(M = Si, Ge; X = Cl) with the diphosphine Ph2P·CH2·CH2PPh2 give ionic complexes [(Ph2P·CH2·CH2·PPh2)Pt(PEt3)MMe3]Cl. With hydrogen chloride in benzene, [(Ph2P·CH2·CH2PPh2)Pt(PEt3)GeMe3]Cl gives the isolable hexaco-ordinate complex [(Ph2P·CH2·CH2·PPh2)Pt(PEte)(H)(Cl)GeMe3]Cl which decomposes in methanol to Me3GeCl and the ionic platinum hydride [(Ph2P·CH2·CH2·PPh2)Pt(PEt3)H]Cl; its decomposition in benzene is more complex. This platinum hydride is more readily prepared by the homogeneous hydrogenolysis of [(Ph2P·CH2·CH2PPh2)Pt(PEt3)MMe3]Cl, M = Si, Ge, in methanol. The 1H n.m.r. and infrared spectra of some of the complexes are described and conductance data are reported. The salts are less rapidly hydrolysed than the neutral complexes and this is interpreted in terms of proton attack at platinum.Keywords
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