Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands

被引:0
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作者
Carter, SM
Lee, J
Hixson, CA
Powell, DR
Wheeler, RA
Shaw, MJ
Richter-Addo, GB
机构
[1] Univ Oklahoma, Dept Chem & Biochem, Norman, OK 73019 USA
[2] Univ Kansas, Dept Chem, Crystallog Lab, Lawrence, KS 66045 USA
[3] So Illinois Univ, Dept Chem, Edwardsville, IL 62026 USA
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中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
We have examined the redox behavior of the osmium and ruthenium compounds (OEP)M(NO)(OEt) and (OEP)M(NO)(SEt) (OEP = octaethylporphyrinato dianion; M = Os, Ru) by cyclic voltammetry and infrared spectroelectrochemistry. The compound (OEP)Os(NO)(OEt) undergoes a single reversible oxidation process in dichloromethane. In contrast, the thiolate compound (OEP)Os(NO)(SEt) undergoes a net irreversible oxidation resulting in formal loss of the SEt ligand. Extended Huckel calculations on crystal structures of these two compounds provide insight into the nature of their HOMOs. In the case of the alkoxide compound, the HOMO is largely metal centered, with 70% of the charge located in the metal's orbital and similar to 25% on the porphyrin ring. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal d(xz) orbital and the p(x) orbital on the sulfur, and a pi antibonding interaction between the metal d orbital and a pi* orbital on NO. The redox behavior of the Ru analogues have been determined, and are compared with those of the Os compounds.
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页码:1338 / 1346
页数:9
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    Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, OK 73019, United States
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