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Syntheses and characterizations of a new valence-averaged mixed-valence diiron complex and a carbonyl derivative of the isovalent diiron complex

Author

Jianhong Zhao, University of the Pacific

Date of Award

1995

Document Type

Thesis - Pacific Access Restricted

Degree Name

Master of Science (M.S.)

Department

Chemistry

First Advisor

Larry Spreer

First Committee Member

Charles A. Matuszak

Second Committee Member

Charles M. McCallum

Abstract

The synthesis and characterization of a new mixed-valence bimetallic iron complex [Fe₂(C₂₀H₃₆N₈)(Cl)₄]⁺ are reported. This binuclear species is assigned as a Robin and Day strongly coupled Class III mixed-valence species based on infrared spectroscopy, cyclic voltammetry, electronic spectroscopy, and X-ray photoelectron spectroscopy. The mixed-valence compound exhibits an intense NIR band at 883 nm with a molar absorptivity of 18000 M^-1cm^-1 and a band width at half-intensity of 2181 cm^-1. This NIR band position Is solvent independent and H_AM is calculated to be 5660 cm^-1. A comproportionation constant of 1.7 x 10¹³ is obtained and this large value indicates that the mixed-valence species is stabilized by delocalization. The XPS results of the mixed-valence compound for the binding energies from Fe 2p_3/2 region show only a single peak, indicating the unpaired electron is delocalized on the short time scale (10^-17 sec) of XPS measurement.

Also a carbonyl derivative of the dimacrocycle bimetallic complex [Fe₂(C₂₀H₃₆N₈)(Cl)₄]⁴⁺ has been isolated and its IR spectrum, electronic spectrum and electrochemical properties have been investigated.

Pages

100

Recommended Citation

Zhao, Jianhong. (1995). Syntheses and characterizations of a new valence-averaged mixed-valence diiron complex and a carbonyl derivative of the isovalent diiron complex. University of the Pacific, Thesis - Pacific Access Restricted. https://scholarlycommons.pacific.edu/uop_etds/2292