Department of Chemistry, Bryn Mawr College, 101 North Merion Avenue, Bryn Mawr, Pennsylvania 19010-2899, USA.
J Am Chem Soc. 2010 Jun 16;132(23):7830-1. doi: 10.1021/ja100220x.
A new monoanionic dithiolene ligand is found in Tp*MoO(S(2)BMOQO). A combination of X-ray crystallography, electronic absorption spectroscopy, resonance Raman spectroscopy, and bonding calculations reveal that the monoanionic dithiolene ligand possesses considerable thiolate-thione character resulting from an admixture of an intraligand charge transfer excited state into the ground state wave function. The unusual dithiolene exhibits a highly versatile donor-acceptor character that dramatically affects the Mo(IV/V) redox couple and points to a potentially noninnocent role of the pterin fragment in pyranopterin Mo enzymes.
Tp*MoO(S(2)BMOQO)中发现了一种新的单核二硫烯配体。X 射线晶体学、电子吸收光谱、共振拉曼光谱和键合计算的组合表明,单核二硫烯配体具有相当大的硫醇盐-硫酮特征,这是由于内配体电荷转移激发态混合到基态波函数中。这种不寻常的二硫烯具有高度多功能的供体-受体特性,这极大地影响了 Mo(IV/V)氧化还原对,并指出蝶呤片段在吡喃并蝶呤 Mo 酶中可能具有非自由基作用。