Relative importance of metal-metal bond scission and loss of carbon monoxide from photoexcited dimanganese decacarbonyl: spectroscopic detection of a coordinatively unsaturated, carbonyl-bridged dinuclear species in low-temperature alkane matrices

Organometallic photochemistry at the end of its first century

“…5. Various studies established that this species reacted with 2-methyltetrahydrofuran, 2-MTHF, to form Mn 2 (CO) 9 (2-MTHF) and with PPh 3 doped matrices to form Mn 2 (CO) 9 (PPh 3 ) [89]. While the Mn(CO) 5 radicals were not observed in these matrix studies (a common feature in frozen matrices due to the rapid recombination of radicals within the solvent cages), they have since been directly observed by time-resolved IR studies [90].…”

“…Proposed mechanism for photochemical carbonylation of alkanes with two photochemical steps [75Photolysis of Mn 2 (CO) 12 in 3-MP[89].…”

Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10

“…Mn 2 (CO) 10 undergoes two distinct wavelength-dependent dissociation pathways in solution. 8,10,13,15,18 The short wavelength absorption band in the UV region has been assigned to a metal-to-ligand chargetransfer (MLCT) state that ultimately induces single carbonyl group loss, producing Mn 2 (CO) 9 in solution. The lower energy band at 374 nm is attributed to the dπ → σ* transition between metal d-orbitals, resulting in enhanced homolytic cleavage of Mn−Mn bonds.…”

Photochemistry and Photophysics of Coordination Compounds

“…There has been considerable interest in the photochemical reaction of metal-metal bonded dimetal carbonyls, L(OC>4M-M(CO) 4 L. Two primary processes, (1) metal-metal bond homolysis to produce radical fragments and (2) CO dissociation without metal-metal bond cleavage, were well established in the cases of M = Mn, L = CO (Yesaka 1981(Yesaka , 1983Rothberg 1982;Hepp 1983;Church 1984) and M=Re, L=CO (Yasufuku 1984).…”