School of Chemistry, University of Southampton, Highfield, Southampton, UKSO17 1BJ.
Dalton Trans. 2009 Sep 21(35):7189-95. doi: 10.1039/b907141p. Epub 2009 Jul 23.
Reactions of Fe(C-N-C)(N2)2, 1a, or Fe(C-NMe-C)(N2)2, 1b, C-N-C = 2,6-bis(arylimidazol-2-ylidene)pyridine, C-NMe-C = 2,6-bis(arylimidazol-2-ylidene)-3,5-dimethylpyridine, aryl = 2,6-iPr2C6H3, with silanes are described. Complex 1a with excess SiPhH3 and complex 1b with excess Si(tol)H3, Ph = phenyl, C6H5, tol = 2-methylphenyl, gave the complexes [Fe(C-N-C)(SiH2Ph)2(2-H-SiH2Ph)], 2a, and [Fe(C-NMe-C)(SiH2tol)2(2-H-SiH2tol)], 2b, respectively. Complex 1b with excess SiPhH3 gave [Fe(C-NMe-C)(SiH2Ph)2(H)2], 3, which was formulated as a dihydride based on the relaxation time T1(min) in the 1H-NMR spectra. Reaction of 1a with SiPh2H2 gave complex [Fe(C-N-C)(SiHPh2)2(2-H2)], 4, while reaction with Si(mes)H3 gave complex [Fe(C-N-C)(SiH2mes)2(N2)], 5, mes = mesityl, 2,4,6-trimethylphenyl. The comparison of the reactivity with other pincer complexes of iron and the mechanism leading to 2a-5 are discussed.
描述了 Fe(C-N-C)(N2)2, 1a，或 Fe(C-NMe-C)(N2)2, 1b 的反应，其中 C-N-C = 2,6-双（芳基咪唑-2-亚基）吡啶，C-NMe-C = 2,6-双（芳基咪唑-2-亚基）-3,5-二甲基吡啶，芳基 = 2,6-异丙基 C6H3，与硅烷反应。1a 与过量的 SiPhH3 和 1b 与过量的 Si(tol)H3（Ph = 苯基，C6H5，tol = 2-甲基苯基）反应，分别得到了配合物 [Fe(C-N-C)(SiH2Ph)2(2-H-SiH2Ph)], 2a 和 [Fe(C-NMe-C)(SiH2tol)2(2-H-SiH2tol)], 2b。1b 与过量的 SiPhH3 反应得到了 [Fe(C-NMe-C)(SiH2Ph)2(H)2]，3，根据 1H-NMR 谱中的弛豫时间 T1(min)，该化合物被认为是二氢化物。1a 与 SiPh2H2 反应得到配合物 [Fe(C-N-C)(SiHPh2)2(2-H2)], 4，而与 Si(mes)H3 反应得到配合物 [Fe(C-N-C)(SiH2mes)2(N2)], 5，mes = 均三甲苯基，2,4,6-三甲基苯基。讨论了与其他铁的钳形配合物的反应性比较以及导致 2a-5 的反应机制。
