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Synthesis and reactivity of thiolate-bridged multi-iron complexes supported by cyclic (alkyl)(amino)carbene

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Indexed by:期刊论文

Date of Publication:2017-12-07

Journal:DALTON TRANSACTIONS

Included Journals:SCIE、EI、PubMed

Volume:46

Issue:45

Page Number:15888-15896

ISSN No.:1477-9226

Abstract: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.

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