Synthesis and electronic characterization of bipyridine dithiolate rhodium(III) complexes

被引:15
作者
Amarante, D
Cherian, C
Catapano, A
Adams, R
Wang, MH
Megehee, EG [1 ]
机构
[1] St Johns Univ, St Johns Coll, Dept Chem, Queens, NY 11439 USA
[2] Columbia Univ Barnard Coll, Dept Chem, New York, NY 10027 USA
关键词
D O I
10.1021/ic051171d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Five new mixed diimine 1,1'-dithiolate or dithiocarbamate ligand complexes of the form [Rh(bpy)(2)(SS)][PF6](n), where bpy = 2,2'-bipyridine and SS = various substituted dialkyldithiocarbamates or 1,1'-dithiolates, were synthesized from cis-[Rh(bpy)(2)(OTf)(2)][OTf]. The triflate ligands are easily displaced by other ligands and allow these syntheses to proceed in high yields (80-90% overall) under relatively mild reaction conditions and to give high purity products. Electrochemistry shows irreversible two-electron reduction of Rh(Ill) to Rh(l) and a concomitant loss of one bipyridine ligand; this is followed by reversible one-electron reduction of the remaining 2,2'-bipyridine ligand. The electronic characterizations of these complexes are consistent with significant delocalization of the sulfur electron density onto the empty metal d orbitals. The 1,1'-dithiolate ligands induce larger red shifts in the absorption and emission spectra than the dithiocarbamates as the 1,1'-dithiolates have a more extensive conjugation system.
引用
收藏
页码:8804 / 8809
页数:6
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