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论文类型：期刊论文

发表时间：2017-12-07

发表刊物：DALTON TRANSACTIONS

收录刊物：SCIE、EI、PubMed

卷号：46

期号：45

页面范围：15888-15896

ISSN号：1477-9226

摘要：The combined utilization of Me-2-cAAC (Me-2-cAAC = : C(CH2)(CMe2)(2)N-2,6-(Pr2C6H3)-Pr-i) and thiolates as supporting ligands enables the access of unprecedented carbene coordinated thiolate-bridged diiron(II) complexes [(Me-2-cAAC)Fe(mu-SR)(Br)](2) (R = Me, 3; R = Et, 4). The coordination environment of each tetrahedral iron(II) center in complexes 3 and 4 is composed of one terminal bromide atom, one carbene carbon atom and two thiolate sulfur atoms, which is similar to the carbide-containing sulfur-rich environment of iron centers in the belt region of the FeMo-cofactor. Interestingly, when NaSCPh3 was chosen as the thiolate ligand, C-S bond homolysis occurred to form a rare [3 : 1] site-differentiated cubane-type cluster [(Me-2-cAAC)Fe4S4(Br)(3)][Me-2-cAACH] (5). Furthermore, complexes 3 and 4 exhibit good exchange reactivity toward the azide anion to give novel thiolate-bridged diiron complexes with two azido ligands in a trans arrangement.