Übergangsmetallphosphidokomplexe. XVII. Reaktionen von Silylphosphanderivaten mit (R3P)2PtCl2 (R = Et,Ph) |
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| Authors: | H Schufer D Binder |
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| Institution: | H. Scháufer,D. Binder |
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| Abstract: | Transition Metal Phosphido Complexes. XVII. Reactions of Silylphosphine Derivatives with (R3P)2PtCl2 (R ? Et, Ph) In reactions of (Et3P)2PtCl2 1a with LiP(SiMe3)2 at low temperatures the substitution products (Et3P)2PtP(SiMe3)2]Cl 2a and (Et3P)2PtP(SiMe3)2]2 3a are formed first. At ambient temperature from 3a P(SiMe3)3 and PEt3 are split off yielding a mixture of the diphosphene complex (Et3P)2Ptη2-(PSiMe3)2] 4a and the phosphido-bridged platinum(I) complex Et3PPtP(SiMe3)2]2(Pt? Pt) 5a . Heating 2a to 80°C in solution gives the P2-complex (Et3P)2Pt]2P2 6a . 4a and 6a are also obtained reacting 1a with (Me3Si)2P]2. From 1a and Me3Si(Me3C)P]2 the diphosphene complex (Et3P)2Ptη2-(PCMe3)2] 8a is available. In the reaction of 1a with (Me3Si)2P? P(CMe3)SiMe3 the formation of the asymmetric diphosphene complex (Et3P)2Ptη2-Me3SiP?PCMe3] 9a can be proved n.m.r. spectroscopically. Analogous reactions of (Ph3P)2PtCl2 1b with LiP(SiMe3)2, and with Me3Si(Me3C)P]2 are much more difficult to survey. The complexes (Ph3P)2Ptη2-(PSiMe3)2] 4b , (Ph3P)2Pt]2P2 6b , and (Ph3P)2Ptη2-(PCMe3)2] 8b are formed in n.m.r. spectroscopically detectable amounts but could not be isolated as pure compounds. N.m.r. and mass spectral data are reported. |
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