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

Dalton Transactions : an International Journal of Inorganic Chemistry
Shawn M CarterG B Richter-Addo

Abstract

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 Hückel 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 approximately 25% on the porphyrin ring. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal dxz orbital and the px 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.

References

Feb 23, 1972·Journal of the American Chemical Society·T S SrivastavaM Tsutsui
Jun 28, 2001·Journal of the American Chemical Society·G B Richter-AddoW R Scheidt
Oct 24, 2001·Inorganic Chemistry·Katrina M. MirandaPeter C. Ford
Mar 28, 1996·Chemical Reviews·Neil G. Connelly, William E. Geiger
Apr 11, 2002·Chemical Reviews·George B Richter-AddoJudith Burstyn
Jul 23, 2003·Biochemistry·Vijay S SharmaDouglas Magde
Apr 27, 2004·Inorganic Chemistry·Cenk SelçukiTimothy Clark

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Citations

Nov 5, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Nan XuGeorge B Richter-Addo
Feb 27, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Dennis AwasabisahGeorge B Richter-Addo

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