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Steric tuning of OH-functionalised N,N-manganese(i) complexes for the transfer hydrogenation of carbonyl compounds
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DOI：10.1039/d6dt00709k.png)
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Abstract
En 中文
A new family of manganese(i) carbonyl complexes, [2-OH-6-{CMe 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 N(2,6-R12-4-R2C6H2)}C5H3N]MnBr(CO)3 (R1 = iPr, R2 = H Mn1a, R1 = iPr, R2 = Br Mn1b, R1 = H, R2 = iPr Mn1d, R1 = H, R2 = Me Mn1e), bearing 6-(arylimino)pyridine N,N-chelating ligands that are appended with a 2-hydroxyl group, have been synthesised and evaluated as catalysts in the transfer hydrogenation (TH) of acetophenone and its derivatives. This set of complexes, differing in their steric and electronic properties of their N-aryl groups, reveal distinct catalytic performances with the least sterically hindered N-4-isopropylphenyl derivative, Mn1d, the most active allowing TON's of up to 1030. Moreover, Mn1d proved highly effective for an assortment of aryl-methyl ketones with the steric/electronic profile of the substrate having an observable effect on conversion. Mechanistic studies involving DFT calculations point towards an outer-sphere mechanism that is distinctly affected by the steric properties of the N-aryl groups of the manganese catalyst.
Keywords:
MOLECULAR-ORBITAL METHODS
BASIS-SETS
MN(I) COMPLEXES
LIGANDS
CO2
CATALYSTS
Journal
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3.3
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3.3W
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7.5W
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