[1+4]-Cycloadditions of silylenes to 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene
[1+4]-Cycloadditions of silylenes to 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene
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DOI：
10.1039/b108020m
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发表时间：
2002-01-01
期刊：
影响因子：
--
通讯作者：
West, R
中科院分区：
文献类型：
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作者：
Clendenning, SB;Gehrhus, B;West, R
2，4，6-三叔丁基-1，3，5-三磷杂苯1与稳定的双(氨基)硅烯Si[(NCH2But)(2)C6H4-1，2]3，Si[(NBut)(2)C2H2]4和Si[(NBut)(2)C2H4]7进行[1+4]-环加成反应，得到结构表征为5，6和11的中间体。通过与[Mo(CO)(4)(Nbd)]反应生成[Mo(CO)(3)(ETA(6)-P3C3Bu3t)](13)和顺式-(14a)和反式-[Mo(CO)(4)(3)(2)](14b)的混合物，证明了5与[Mo(CO)(4)(Nbd)]反应的可逆性。
2,4,6-Tri-tert-butyl-1,3,5-triphosphabenzene 1 undergoes [1 + 4]-cycloaddition with the stable bis(amino)silylenes Si[(NCH2But)(2)C6H4-1,2] 3, Si[(NBut)(2)C2H2] 4 and Si[(NBut)(2)C2H4] 7 to afford the structurally characterised 5, 6 and 11. The intermediate aminosilylsilylene resulting from the dissociation of the disilene [Si{(NBut)(2)C2H4}](4) 9 was trapped as its [1 + 4]-cycloadduct with 1, which was also structurally characterised. The reversibility of the cycloaddition was demonstrated for 5 through reaction with [Mo(CO)(4)(nbd)] to afford [Mo(CO)(3)(eta(6)-P3C3Bu3t)] (13) and a mixture of cis- (14a) and trans-[Mo(CO)(4)(3)(2)] (14b) of which 14b has been structurally characterised by a single crystal X-ray diffraction study.