Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
Inorg Chem. 2013 Jul 15;52(14):8218-27. doi: 10.1021/ic401096p. Epub 2013 Jun 21.
Thermolysis of Fe(N═C(t)Bu2)4 (1) for 8 h at 50 °C generates the mixed valent Fe(III)/Fe(II) bimetallic complex Fe2(N═C(t)Bu2)5 (2) in moderate yield. Also formed in this reaction are tert-butyl cyanide, isobutane, and isobutylene, the products of ketimide oxidation by the Fe(4+) center. Reaction of 1 with 1 equiv of acetylacetone affords the Fe(III) complex, Fe(N═C(t)Bu2)2(acac) (3), concomitant with formation of bis(tert-butyl)ketimine, tert-butyl cyanide, isobutane, and isobutylene. In addition, the Mössbauer spectra of 1 and its lower-valent analogues [Li(12-crown-4)2][Fe(N═C(t)Bu2)4] (5) and [Li(THF)]2[Fe(N═C(t)Bu2)4] (6) were recorded. We also revisited the chemistry of Fe(1-norbornyl)4 (4) to elucidate its solid-state molecular structure and determine its Mössbauer spectrum, for comparison with that recorded for 1.
将 Fe(N═C(t)Bu2)4（1）在 50°C 下热解 8 小时，可中等产率地生成混合价态的 Fe(III)/Fe(II) 双金属配合物 Fe2(N═C(t)Bu2)5（2）。该反应还生成叔丁基氰、异丁烷和异丁烯，它们是 Fe(4+)中心氧化酰亚胺的产物。1 与 1 当量的乙酰丙酮反应生成 Fe(III)配合物 Fe(N═C(t)Bu2)2(acac)（3），同时形成双（叔丁基）亚胺、叔丁基氰、异丁烷和异丁烯。此外，还记录了 1 及其低价类似物[Li(12-冠-4)2][Fe(N═C(t)Bu2)4]（5）和[Li(THF)]2[Fe(N═C(t)Bu2)4]（6）的 Mössbauer 光谱。我们还重新研究了 Fe(1-降冰片基)4（4）的化学性质，以阐明其固态分子结构，并确定其 Mössbauer 光谱，以便与 1 的记录进行比较。
