新型{Fe(NO)2}10 二硝酰基铁配合物与[硫醇盐、硫醇盐]和[酰胺、酰胺]配体结合。

New members of the {Fe(NO)2}10 dinitrosyliron complexes bound with [thiolate, thiolate] and [amide, amide] ligations.

机构信息

School of Applied Chemistry, Chung Shan Medical University, Taichung City 40201, Taiwan.

出版信息

Inorg Chem. 2010 Sep 6;49(17):7644-6. doi: 10.1021/ic101126v.

PMID:20687531

Abstract

The first dianionic {Fe(NO)(2)}(10) dinitrosyliron complexes (DNICs) Fe(SC(7)H(4)SN)(2)(NO)(2) (1) and Fe(OC(7)H(4)SN)(2)(NO)(2) (2), coordinated with thiolates and amides, were prepared by the reaction of Fe(TMEDA)(NO)(2) with 2 equiv of ligands SC(7)H(4)SN and OC(7)H(4)SN, respectively. The reversible interconversion between the dianionic {Fe(NO)(2)}(10) DNICs 1/2 and the anionic {Fe(NO)(2)}(9)Fe(SC(7)H(4)SN)(2)(NO)(2) (3)/Fe(OC(7)H(4)SN)(2)(NO)(2) (4), respectively, was demonstrated. The transformation of DNICs 2 and 3 into the thermally stable DNICs 1 and 4, respectively, via the ligand-exchange reaction reveals that OC(7)H(4)SN shows a high binding affinity toward the {Fe(NO)(2)}(9) motif and SC(7)H(4)SN prefers the {Fe(NO)(2)}(10) motif. This result rationalizes that the intermolecular electron transfer from DNIC 2 to DNIC 3 occurs to lead to the formation of the more thermally stable DNICs 1 and 4 upon the reaction of DNICs 2 and 3 in tetrahydrofuran.

摘要

具有硫醇和酰胺配体的首例二价铁（Fe(NO)(2)）（10）双氮基铁配合物（DNIC）Fe(SC(7)H(4)SN)(2)(NO)(2)（1）和Fe(OC(7)H(4)SN)(2)(NO)(2)（2），通过 Fe(TMEDA)(NO)(2)与 2 当量的配体SC(7)H(4)SN和OC(7)H(4)SN反应制备。二价铁（Fe(NO)(2)）（10）DNICs 1/2 和阴离子{Fe(NO)(2)}(9)Fe(SC(7)H(4)SN)(2)(NO)(2)（3）/Fe(OC(7)H(4)SN)(2)(NO)(2)（4）之间的可逆相互转化得到了证明。DNICs 2 和 3 通过配体交换反应分别转化为热稳定的 DNICs 1 和 4，表明OC(7)H(4)SN对{Fe(NO)(2)}(9)基序具有高的结合亲和力，而SC(7)H(4)SN则更喜欢{Fe(NO)(2)}(10)基序。这一结果合理地解释了在四氢呋喃中二价铁（Fe(NO)(2)）（10）DNIC 2 和 3 的分子间电子转移发生，导致在二价铁（Fe(NO)(2)）（10）DNIC 2 和 3 的反应中形成更热稳定的二价铁（Fe(NO)(2)）（10）DNIC 1 和 4。