Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
J Am Chem Soc. 2010 Nov 17;132(45):15884-6. doi: 10.1021/ja106478k. Epub 2010 Oct 26.
The dinuclear precursors Fe(2)(N(t)Bu)(2)Cl(2)(NH(2)(t)Bu)(2), Fe(2)(N(t)Bu)(S)Cl(4), and Fe(2)(NH(t)Bu)(2)(S)(N{SiMe(3)}(2))(2) allowed the selective syntheses of the cubane clusters Fe(4)(N(t)Bu)(n)(S)(4-n)Cl(4) with [n, z] = [3, 1-], [2, 2-], [1, 2-]. Weak-field iron-sulfur clusters with heteroleptic, nitrogen-containing cores are of interest with respect to observed or conjectured environments in the iron-molybdenum cofactor of nitrogenase. In this context, the present iron-imide-sulfide clusters constitute a new class of compounds for study, with the Fe(4)NS(3) core of the [1, 2-] cluster affording the first synthetic representation of the corresponding heteroligated Fe(4)S(3)X subunit in the cofactor.
双核前体 Fe(2)(N(t)Bu)(2)Cl(2)(NH(2)(t)Bu)(2)、Fe(2)(N(t)Bu)(S)Cl(4) 和 Fe(2)(NH(t)Bu)(2)(S)(N{SiMe(3)}(2))(2) 允许选择性合成笼形簇 Fe(4)(N(t)Bu)(n)(S)(4-n)Cl(4)，其中 [n, z] = [3, 1-]、[2, 2-]、[1, 2-]。具有杂配位、含氮核的弱场铁硫簇在固氮酶铁钼辅因子中观察到或推测的环境方面具有重要意义。在这种情况下，本研究中的铁亚胺-硫簇构成了一类新的化合物，[1, 2-]簇的 Fe(4)NS(3)核提供了辅因子中相应异配位 Fe(4)S(3)X 亚基的第一个合成代表。
