School of Chemistry, University of Tasmania, Hobart, Tasmania, Australia.
Dalton Trans. 2010 Aug 7;39(29):6864-70. doi: 10.1039/c002778b. Epub 2010 Jun 3.
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[triple bond]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[triple bond]N forms Sm(II) adducts that undergo reductive C-C bond cleavage at elevated temperatures to afford a trimeric Sm(III) cyanide (mu-C[triple bond]N(-)) complex. The isomeric isonitrile t-BuN[triple bond]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.
二价钐的 N,N'-二甲基金属化卟啉原配合物与一系列叔丁基取代的杂炔反应，表现出多样化的反应性。膦炔 t-BuC[三重键]P 生成具有新的 μ-η(2)(1,2-C,P)键合模式的双核 Sm(III) P-P 还原偶联配合物(t-BuC=PP=C-t-Bu)(2-)。相比之下，腈亚胺类似物 t-BuC[三重键]N 形成 Sm(II)加合物，在较高温度下经历还原 C-C 键断裂，生成三聚体 Sm(III)氰化物(μ-C[三重键]N(-))配合物。异构体异腈 t-BuN[三重键]C 在较温和的温度下经历相关的还原 C-N 键断裂反应性，允许捕获叔丁基片段作为 Sm(III)η(2)-亚氨基甲酰(t-BuC=N-t-Bu)(-)配合物。
