Sm(II) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C-C/C-N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitriles
Sm(II) reduction chemistry of heteroalkynes: stable adducts, reductive coupling, reductive C-C/C-N bond cleavage and trapping of the tert-butyl fragment with bulky nitriles, phosphaalkynes and isonitriles
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DOI：
10.1039/c002778b
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发表时间：
2010-01-01
影响因子：
4
通讯作者：
Schulten, Christian
中科院分区：
文献类型：
--
作者：
Gardiner, Michael G.;James, Adam N.;Schulten, Christian
双金属N，N‘-二甲基取代卟啉Sm(II)与一系列叔丁基取代杂炔的反应提供了不同范围的反应活性。T-Buc-P是一种双核Sm(III)P-P还原偶联络合物(t-Buc=PP=C-t-Bu)(2-)，具有新的Mu-ETA(2)(1，2-C，P)结合方式。相反，腈氮杂类似物t-Buc N形成Sm(II)加合物，这些加合物在高温下经历还原的C-C键断裂，得到三聚体Sm(III)氰化物(Mu-C N(-))。异构体t-Bun C在较温和的温度下经历相关的还原C-N键裂解反应，允许叔丁基片段以Sm(III)ETA(2)-亚氨基酰基(t-Buc=N-t-Bu)(-)络合物的形式被捕获。
Reactions of a dimetallated N,N'-dimethyl substituted porphyrinogen Sm(II) complex with a series of t-butyl substituted heteroalkynes affords a diverse range of reactivity. The phosphaalkyne t-BuC P gives a dinuclear Sm(III) P-P reductively coupled complex of (t-BuC=PP=C-t-Bu)(2-) featuring a new mu-eta(2)(1,2-C,P) binding mode. In contrast, the nitrile aza analogue t-BuC N forms Sm(II) adducts that undergo reductive C-C bond cleavage at elevated temperatures to afford a trimeric Sm( III) cyanide (mu-C N(-)) complex. The isomeric isonitrile t-BuN C undergoes the related reductive C-N bond cleavage reactivity at milder temperatures, allowing the trapping of the tert-butyl fragment as a Sm(III) eta(2)-iminoacyl (t-BuC=N-t-Bu)(-) complex.