Add time:07/31/2019         Source:sciencedirect.com

Bimetallic alkoxides of praseodymium and neodymium with aluminum, viz., M[Al(OC3Hi7)4]3, where M = Pr(III)/Nd(III), have been used as catalysts in Meerwein–Ponndorf–Verley (MPV) reduction of 2-octanone and benzophenone in isopropanol to give their corresponding secondary alcohols. The reduction of ketones is investigated by following the absorption spectra involving 4f–4f transitions. During the MPV reduction the oscillator strengths (P) and the Judd–Ofelt intensity (Tλ, λ=2,4,6) parameters corresponding to each 4f–4f band (H43→D21, H43→P03, H43→P13, and H43→P23 in praseodymium, and I9/24→F3/24, I9/24→F5/24, I9/24→F7/24, I9/24→G5/24, and I9/24→G7/24 in neodymium alkoxides) at different time intervals have also been calculated and used in the determination of rates. Rates were calculated in terms of complexation of ketone and isopropanol with M[Al(OC3Hi7)4]3 during the MPV reaction, from the changes in both absorbance and oscillator strength with time, and were found to be comparable, verifying the Judd–Ofelt theory. The stronger oxyphilicity of Pr(III) and Nd(III) in M[Al(OC3Hi7)4]3 than of their analogue Al(III) in Al(OC3Hi7)3 made the bimetallic alkoxides better catalyst in MPV reduction of ketones.

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