Selective formation of cis-(HMe2Si)2Pt(PEt3)2 from HMe2SiSiMe2H and Pt(PEt3)3 and its reactivities relevant to generation of (silylene)platinum species thereof
Selective formation of cis-(HMe2Si)2Pt(PEt3)2 from HMe2SiSiMe2H and Pt(PEt3)3 and its reactivities relevant to generation of (silylene)platinum species thereof
复制标题
从 HMe2SiSiMe2H 和 Pt(PEt3)3 选择性形成顺式-(HMe2Si)2Pt(PEt3)2 及其与其生成(亚硅基)铂物种相关的反应性
DOI：
10.1021/om00046a019
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发表时间：
1992
期刊：
影响因子：
2.8
通讯作者：
M. Goto
中科院分区：
文献类型：
--
作者：
H. Yamashita;Masato Tanaka;M. Goto
hme2siisime2h （1,3 equiv）在室温下与Pt (PEt3) 3反应得到cts-(HMe2Si) 2Pt (PEt3) 2(2)和HtSiMe^ JH(1<< 7)，而2则由1 （1 equiv）与Pt (PEta) 3在30 eC下选择性反应得到。在室温下，当用PtíPEt^处理HMe^ iSiMes或H2MeSiSiMe3时，也能产生低聚物再分配产物，尽管没有发现Si-Pi物种。1在室温下被2有效地催化重新分配，得到HtSiMe^ H，其摩尔比为> 30:10:30:5:2:1:3 0 =1-7。Me2SiH2主要由2在60℃时热裂解生成。2与苯乙炔（3等温）在60℃下反应得到4,4 -二甲基- 2,6 -二苯基-l-铂-4-硅- 2,5 -环己二烯(4)，x射线晶体分析确定其结构为：空间群P2l/n， a- 12.319 (1) a, b= 20.164 (1) a, C = 12.837 (2) a， ß= 97.03 (1)， V= 3164.8 (7) A1 23， Z= 4。在120℃下加热得到的唯一挥发产物为1,1 -二甲基- 3,4 -二苯基- 1,4 -硅- 2,4 -环戊二烯。
HMe2SiSiMe2H (1, 3 equiv) reacted with Pt (PEt3) 3 at room temperature to give cts-(HMe2Si) 2Pt (PEt3) 2 (2) and oligoeilanes HtSiMe^ JH (1<< 7), while 2was selectively obtained by the reaction of 1 (1 equiv) with Pt (PEta) 3 at-30 eC. HMe^ iSiMes or H2MeSiSiMe3 also afforded oligomeric redistribution products when treated with PtíPEt^ at room temperature, although Si-Pi species were not found. Redistribution of 1 was efficiently catalyzed by 2 at room temperature, leading to HtSiMe^ H with the approximate molar ratio being> 30: 10: 30: 5: 2: 1: 0.3 for=1-7, respectively. Me2SiH2 was mainly formed upon thermolysis of 2 at 60 eC. Reaction of 2 with phenylacetylene (3 equiv) at 60 C gave 4, 4-dimethyl-2, 6-diphenyl-l-platina-4-sila-2, 5-cydohexadiene (4), the structure of which was determined by X-ray crystallographic analysis: space group P2l/n, a- 12.319 (1) A, b= 20.164 (1) A, c= 12.837 (2) A, ß= 97.03 (1), V= 3164.8 (7) A1 23, Z= 4. Heating 4 at 120 C afforded l, l-dimethyl-3, 4-diphenyl-l-sila-2, 4-cyclopentadiene as the sole volatile product.