Electronic structure of bent titanocene complexes with chelated dithiolate ligands

被引：24

作者：

Cooney, JJA ^{[1
]}

Cranswick, MA ^{[1
]}

Gruhn, NE ^{[1
]}

Joshi, HK ^{[1
]}

Enemark, JH ^{[1
]}

机构：

[1] Univ Arizona, Dept Chem, Tucson, AZ 85721 USA

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 25期

关键词：

D O I：

10.1021/ic049207+

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Gas-phase photoelectron spectroscopy and density functional theory have been utilized to investigate the interactions between the p orbitals of dithiolate ligands and d orbitals of titanium in bent titanocene complexes as minimum molecular models of active site features of pyranopterin Mo/W enzymes. The compounds Cp2Ti(S-S) [where (S-S) is 1,2-ethenedithiolate (S2C2H2), 1, 1,2-benzenedithiolate (bdt), 2, or 1,3-propanedithiolate (pdt), 3, and Cp- is cyclopentadienyl] provide access to a formal 16-electron d(0) electronic configuration at the metal. A "dithiolate-folding-effect" involving an interaction of metal and sulfur orbitals is demonstrated in complexes with arene- and enedithiolates. This effect is not observed for the alkanedithiolate in complex 3.

引用

页码：8110 / 8118

页数：9

共 56 条

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