Syntheses, spectroscopic characteristics and thermolytic rearrangements of bis-[(trimethylgermyl)methyl]platinum(II) and bis-[(trimethylstannyl)methyl]platinum(II) complexes
作者:Victor Christou、G.Brent Young
DOI:10.1016/0022-328x(95)05908-8
日期:1996.3
lower activation enthalpy. While cis-Pt(CH2GeMe3)2(PPh2Me)2 reacts similarly but less readily, Pt(CH2GeMe3)2(dppe)2 is inert at operable temperatures. Thermolysis of Pt(CH2GeMe3)2(cod) generates 1,1,3,3,-tetramethyldi-1,3-germacyclobutane as the major organogermanium product, while from cis-Pt(CH2SnMe3)2(PPh3)2, 1,1,3,3-tetramethyldi-1,3-stannacyclobutane predominates. Mechanistic implications are discussed
报道了一系列具有三烯和P-供体辅助配体的顺式-Pt(CH 2 GeMe 3)2 L 2(L = PPh )的(三甲基锗烷基)甲基-和(三甲基锡烷基)甲基铂(II)配合物的制备和光谱特征。3或PPh 2 Me; L 2 = dppe或cod)和顺式-Pt(CH 2 SnMe 3)2 L 2(L = PPh 3; L 2 = cod)。顺式-Pt(CH 2 GeMe 3)甲苯溶液的热解2(PPh 3)2在(非限速)膦分解后,经由β-烷基迁移导致顺式-Pt(Me)(CH 2 GeMe 2 CH 2 GeMe 3)(PPh 3)2。估计的活化参数(ΔH 298 K ‡ = 126±3 kJ mol -1,ΔS ‡ = + 17±7 J mol -1 K -1,因此Δ298 K ‡ = 121±5 kJ mol -1)表明,该系统比其硅类似物的迁移更加不稳定,这主要是由于较低的活化焓所致。而顺式-Pt(CH