Trimethyl-silyl, -germyl and -stannyl complexes of platinum

A. Clemmit, F. Glockling
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引用次数: 19

Abstract

Two series of compounds (chelate)PtCl(MMe3)(I) and (chelate)Pt(MMe3)2(II)[chelate =(Ph2PCH2)2; M = Si, Ge, or Sn] have been isolated. For M = Si or Ge both are obtained by the reaction of (chelate)PtCl2 with (Me3M)2Hg. Trimethylstannyl–platinum compounds have been isolated (a) by exchange reactions e.g. Pt–MMe3+ Me3SnH → Pt–SnMe3+ Me3MH (M = Si, Ge) and (b) from the oxidative addition of Me3SnH to (chelate)2Pt. Trimethylstannane adds reversibly to (I) and (II) when M = Sn yielding the octahedral complexes (chelate)Pt(H)(Cl)(SnMe3)2 and (chelate)Pt(H)(SnMe3)3 respectively. Stepwise hydrogen chloride cleavage of Pt–MMe3 groups has been investigated: the products from (chelate)Pt(MMe3)2 are (chelate)PtCl(MMe3) and (chelate)PtCl2. Hydrogenolysis of Pt–MMe3 bonds proceeds readily when M = Si or Ge (1 atmos. H2 and 25°). For the reaction (chelate)Pt(SiMe3)2+ H2→(chelate)PtH(SiMe3) the rate constant at 25° is ca. 5·0 × 10–2 l mol–1 s–1, the reaction being first-order with respect to H2 and (II). At 70° and 1 atoms. H2 the second Me3Si–Pt bond is hydrogenated to Me3SiH and a platinum cluster compound, formulated as (chelate)3Pt4. Equilibrium constants have been derived for the hydrogenolysis of trans-(Et3P)2PtCl(SiMe3). Exchange reactions of the types: Pt–SiMe3+ Me3GeH → Pt–GeMe3+ Me3SiH and Pt–GeMe3+ Me3SnH → Pt–SnMe3+ Me3GeH have been investigated; the position of equilibrium favours R3M–Pt products in the order, Sn Ge > Si. Cleavage of Pt–M bonds by 1,2-dibromoethane is considered to involve an octahedral intermediate. 1H n.m.r., i.r. and mass spectra of the various compounds and reactions are discussed.
铂的三甲基硅基、-丁基和-锡基配合物
两个系列的化合物(螯合)PtCl(MMe3)(I)和(螯合)Pt(MMe3)2(II)[螯合=(Ph2PCH2)2;M = Si, Ge, Sn]已被分离。对于M = Si或Ge,两者都是由(螯合)PtCl2与(Me3M)2Hg反应得到的。三甲基锡基铂化合物通过(a)交换反应分离得到,例如Pt-MMe3 + Me3SnH→Pt-SnMe3 + Me3MH (M = Si, Ge)和(b) Me3SnH氧化加成(螯合)2Pt。当M = Sn时,三甲基锡烷可逆地加入(I)和(II),分别生成八面体配合物(螯合)Pt(H)(Cl)(SnMe3)2和(螯合)Pt(H)(SnMe3)3。研究了氯化氢对Pt - MMe3基团的分步切割:(螯合)Pt(MMe3)2的产物是(螯合)PtCl(MMe3)和(螯合)PtCl2。当M = Si或Ge (1atmos)时,Pt-MMe3键的氢解容易进行。H2和25°)。对于(螯合)Pt(SiMe3)2+ H2→(螯合)PtH(SiMe3)反应,在25°时的速率常数约为5·0 × 10-2 l mol-1 s-1,在70°和1个原子时,反应是一级反应。第二个Me3Si-Pt键氢化成Me3SiH和铂簇化合物,形成(螯合物)3Pt4。推导了反式-(Et3P)2PtCl(SiMe3)氢解反应的平衡常数。研究了Pt-SiMe3 + Me3GeH→Pt-GeMe3 + Me3SiH和Pt-GeMe3 + Me3SnH→Pt-SnMe3 + Me3GeH的交换反应;平衡位置有利于R3M-Pt产物,顺序为Sn - Ge > Si。1,2-二溴乙烷对Pt-M键的裂解被认为涉及一个八面体中间体。讨论了各种化合物和反应的1H、nmr、ir和质谱。
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