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For a series of singly arsenic bridged dinuclear metal carbonyl complexes with metal-metal bonds electronic spectra and dc-voltammograms in 1,2-dichloroethane were recorded. There is a reasonable correlation between the σ→σ* transitions and the first reduction potentials which can both be taken as measures of the relative strength of the metal-metal bonds. The σ→σ* excitation energy and the negative reduction potential increase (a) with increasing atomic weight of the connected metal atoms, (b) with in­creasing number of CO groups present, (c) with decreasing intramolecular steric hindrance. Steric and electronic factors cannot be cleanly separated. There seems to be no correlation with metal-metal bond lengths. Terminal phosphine ligands decrease all redox potentials but hardly change the electronic absorptions.

zeitschrift für naturforschung b

Elektrochemische und elektronenspektroskopische Messungen zur Natur einfach arsenverbriickter Metall-Metall-Bindungen/Electrochemical and Electron Spectroscopic Measurements on the Nature of Singly Arsenic Bridged Metal-Metal Bonds