ester with the fully delocalized mixed-valence core. The complete bridged-thiolate cleavage yielded DNIC [(EtS) 2Fe(NO) 2] (-) ( 3a) in the reaction of 2 equiv of [EtS] (-) and complex 1a, whereas reaction of 2 equiv of [(t)BuS] (-) with [Fe(micro-S (t)Bu)(NO) 2] 2 (1b) gave DNIC [((t)BuS) 2Fe(NO) 2] (-) (3b) and the anionic Roussin's red ester [Fe(mu-S (t)Bu)(NO) 2] 2 (-) (2b) through bridged-thiolate
合成了阴离子顺-/反-[Fe(mu-
SEt)(NO)2] 2(-)(2a)并通过红外,紫外可见,EPR和X射线衍射进行了表征。[Fe(mu-S)2Fe]核的几何形状从[Fe(NO)2}(9)-Fe(NO)2}(9)]鲁辛红酯[Fe(mu-
SEt)(NO)2] 2(1a)(Fe ... Fe距离为2.7080(5)A)至[Fe(NO)2}(9)-Fe(NO)2}(10)]络合物2a(Fe ... Fe距离为2.8413(6)A)以最小化Fe ... Fe相互作用的程度来稳定络合物2a。根据X射线吸收(Fe K边缘和L边缘),EPR和SQUID,最好将配合物2a描述为阴离子[Fe(NO)2}(9)-Fe(NO)2}( 10)]带有完全离域混合价核的鲁辛红酯。在2当量的[EtS](-)与络合物1a反应中,完全桥连的
硫醇盐裂解生成DNIC [(EtS)2Fe(NO)2](-)(3a)