Bromotricarbonyldi(Pyridine)Manganese(I)

Pons, M D. Torres; Herberich, Gerhard E.; Kirk, Patrick N.; Castellani, Michael P.; Rizzo, Michael J.; Atwood, Jim D.

doi:10.1002/9781118744994.ch28

Cited by 4 publications

(1 citation statement)

References 11 publications

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“…Manganese pentacarbonyl bromide (98%, Beantown Chemical Co.), 2,2′-bipyridyl (bpy; 98%; Alfa Aesar), 4,4′-di- tert -butylbipyridine ( t Bu-bpy; 98%, Sigma-Aldrich), 2-chloro-4-(trifluoromethyl)pyridine (98%; Oakwood Chemical), fuming nitric acid (90%, Alfa Aesar), and PCl 3 (98%, Alfa Aesar) were used as received. 2,2′-Bipyridyl N , N ′-dioxide, 4,4′-dinitro-2,2′-bipyridyl N , N ′-dioxide, 4,4′-dinitro-2,2′-bipyridyl (dnbpy), 4,4′-bis(trifluoromethyl)-2,2′-bipyridyl (CF 3 -bpy), Mn(CO) 3 Br(pyridine) 2 , Mn(CO) 3 Br(bpy), and Mn(CO) 3 Br[4,4′-bis( tert -butyl)-2,2′-bipyridyl] were prepared according to literature methods with minor modifications. If necessary, the ligands bpy, t Bu-bpy, and CF 3 -bpy can be sublimed (at ca.…”

Section: Methodsmentioning

confidence: 99%

Ultrafast Spectroscopy of [Mn(CO)₃] Complexes: Tuning the Kinetics of Light-Driven CO Release and Solvent Binding

et al. 2020

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Manganese tricarbonyl complexes are promising catalysts for CO 2 reduction, but complexes in this family are often photo-sensitive and decompose rapidly upon exposure to visible light. In this report, synthetic and photochemical studies probe the initial steps of light-driven speciation for Mn(CO) 3 ( R bpy)Br complexes bearing a range of 4,4′-disubstituted-2,2′-bipyridyl ligands ( R bpy, R = t Bu, H, CF 3 , NO 2 ). Transient absorption spectroscopy measurements for the Mn(CO) 3 ( R bpy)Br coordination compounds with R = t Bu, H, and CF 3 in acetonitrile reveal ultrafast loss of a CO ligand on the femtosecond timescale, followed by solvent coordination on the picosecond timescale. The Mn(CO) 3 ( NO2 bpy)Br complex is unique among the four compounds in having a longer-lived excited state that does not undergo CO release or the subsequent solvent coordination. The kinetics of photolysis and solvent coordination for the lightsensitive complexes depend on the electronic properties of the di-substituted bipyridyl ligand. The results implicate roles for both metal-to-ligand charge transfer (MLCT) and dissociative ligand field (dd) excited states in the ultrafast photochemistry. Taken together, the findings suggest that more robust catalysts could be prepared with appropriately designed complexes that avoid crossing between the excited states that drive photochemical CO loss.

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