Photochemical reactivity of two gold(I) dinuclear complexes, cis/trans-(AupNBT)2dppee: Isomerization for the cis-(AupNBT)2dppee isomer, radical substitution for trans-(AupNBT)2dppee

Two complexes, cis (1) and trans (2) (AupNBT)(2)dppee (pNBT = p-nitrobenzenethiol; dppee = bis(diphenylphosphino)ethylene) have been synthesized and characterized. X-ray diffraction studies reveal that cis-(AupNBT)(2)dppee has an intramolecular gold-gold distance of 3.0036(3) angstrom while the trans-(AupNBT)(2)dppee crystal is a dimer with an intermolecular gold-gold distance of 3.1201(4) angstrom. We have used UV-Vis spectroscopy, H-1 NMR, and P-31 {H-1} NMR to investigate the photochemical reactivity of both complexes. In a range of organic solvents with lambda > 230 nm cis-(AupNBT)(2)dppee readily isomerizes to the trans isomer. Under these same conditions, the trans isomer does not isomerize to cis-(AupNBT)(2)dppee, but undergoes a photochemical substitution reaction. In chlorinated solvents (CH2Cl2, CH3Cl) trans-(AupNBT)(2)dppee reacts to form trans-(AuCl)(2)dppee (3) which crystallizes into an extended chain of molecules linked via intermolecular gold-gold distances of 3.0203(2) angstrom. TDDFT calculations support the observed experimental results. We propose that at high energies the reaction is initiated by chlorine radicals from direct photolysis of the solvent. At longer wavelengths the excited state of the metal complex is the photoactive species, abstracting a chlorine radical from the solvent. (C) 2012 Elsevier B.V. All rights reserved.