Photochemistry of Metal—Metal—Bonded Transition Element Complexes

Photoinduced Electron Transfer via Nonbuttressed Metal−Metal Bonds. The Photochemical Study of Binuclear Complexes with Platinum−Thallium Bonds

“…This situation is not unusual. It has been observed for a series of heteronuclear carbonyl compounds with metal−metal bonds between transition and main group IV metals that M−M′ bonds are not efficiently cleaved compared to the disruption of the M−CO bonds …”

“…The number of experimentally proven examples of the photoinduced heterolysis is, however, very limited. To the best of our knowledge, the heterolytic scission of the dative metal-metal bond has been confirmed only for CofAu and OsfW linkages in [Ph 3 PAu-Co(CO) 4 ] 5 and [(Me 3 P)(OC) 4 Os-W(CO) 5 ] 8 complexes, respectively.…”

“…Photochemical investigations on nonsupported metal−metal bonds have been mostly carried out on carbonyl-containing metal−metal bonded homonuclear dimers, M−M. – Several instances of photosensitive heterobinuclear organometallic compounds with dative covalent bonds, M→M′, have been also reported. – Irradiation of the homonuclear dimers generally leads to either metal−metal bond homolysis or metal−ligand bond dissociation . Molecules with metal−metal dative bonds are of special interest since photolysis may result in heterolytic cleavage of the M→M′ bonds.…”

Photochemical behavior of the quadruply metal-metal bonded [Tc2Cl8]2− anion in acetonitrile

“…For Re, the photochemistry of [Re 2 Cl 8 ] 2has been extensively studied [8,9,10,11]. The speciation of Tc before and after irradiation has been studied by UV-visible spectroscopy.…”

Photoredox Chemistry of d4 Bimetallic Systems

“…For the d 7 complexes, irradiation of metal-localized σ -• σ* and π -• σ* transitions typically results in the cleavage of the metal-metal bond to produce a "dissociative diradical" pair (·Μ, Μ·, Figure la) (5)(6)(7)(8)(9). Conversely, excitation of the lowest energy da* -+ πσ transition of d 8 ---d 8 complexes (10)(11)(12) yields an "associative diradical" pair (·Μ-Μ·, Figure lb) wherein the electrons of this triplet-configured lowest-energy excited state are localized formally on the metal atoms (11)(12)(13)(14).…”