Subtle bite-angle influences on N2S2Ni complexes

被引：58

作者：

Smee, JJ ^{[1
]}

Miller, ML ^{[1
]}

Grapperhaus, CA ^{[1
]}

Reibenspies, JH ^{[1
]}

Darensbourg, MY ^{[1
]}

机构：

[1] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

来源：

INORGANIC CHEMISTRY | 2001年 / 40卷 / 14期

关键词：

D O I：

10.1021/ic0008619

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new N2S2Ni complex based on the 1,4-diazacycloheptane (dach) framework allows the study of the effects of ring size, in fused diamines, on the structural and chemical properties of nickel(II) dithiolate and dithioether complexes. Compared to its 1,5-diazacyclooctane (daco) derivatives, the dithiolate complex (bmedach)Ni and the S-templated, macrocyclic dithioether complex (propyl-bmedach)NiBr2 show decreased cavity sizes with narrower <N-Ni-N angles (by ca. 6 degrees) and wider <S-Ni-S angles (also by ca. 6 degrees). The electrochemical properties of the dithiolate complexes based on dach and daco are nearly identical, while the (propyl-bmedach)NiBr2 complex shows a 140 mV destabilization of the Ni-I oxidation state relative to its daco analogue. Molecular structures for the (bmedach)Ni and (propyl-bmedach)NiBr2 complexes and their respective electrochemical and spectroscopic properties are reported.

引用

页码：3601 / 3605

页数：5

共 21 条

[1] DESTABILIZING D-PI-P-PI ORBITAL INTERACTIONS AND THE ALKYLATION REACTIONS OF IRON(II) THIOLATE COMPLEXES [J].