Synthesis and characterization of chiral phosphirane derivatives of [(μ-H)4Ru4(CO)12] and their application in the hydrogenation of an α,β-unsaturated carboxylic acid

4 years ago

Synthesis and characterization of chiral phosphirane derivatives of [(μ-H)4Ru4(CO)12] and their application in the hydrogenation of an α,β-unsaturated carboxylic acid

Ruthenium clusters containing the chiral binaphthyl-derived mono-phosphiranes [(S)-([1,1′-binaphthalen]-2-yl)phosphirane] (S)-1a, [(R)-(2′-methoxy-1,1′-binaphthyl-2-yl)phosphirane] (R)-1b, and the diphosphirane [2,2′-di(phosphiran-1-yl)-1,1′-binaphthalene] (S)-1c have been synthesized and characterized. The clusters are [(μ-H)4Ru4(CO)11((S)-1a)] (S)-2, [(μ-H)4Ru4(CO)11((R)-1b)] (R)-3, 1,1-[(μ-H)4Ru4(CO)10((S)-1c)] (S)-4, [(μ-H)4Ru4(CO)11((S)-binaphthyl-P(s)(H)Et)] (S,S p)-5, [(μ-H)4Ru4(CO)11((S)-binaphthyl-P(R)(H)Et)] (S,R p)-6, [(μ-H)4Ru4(CO)11((R)-binaphthyl-P(s)(H)Et)] (R,S p)-7, [(μ-H)4Ru4(CO)11((R)-binaphthyl-P(R)(H)Et)] (R,R p)-8 and the phosphinidene-capped triruthenium cluster [(μ-H)2Ru3(CO)9(PEt)] 9. Clusters 5–8 are formed via hydrogenation and opening of the phosphirane ring in clusters (S)-2 and (R)-3. The phosphirane-substituted clusters were found to be able to catalyze the hydrogenation of trans-2-methyl-2-butenoic acid (tiglic acid), but no enantioselectivity could be detected. The molecular structures of (S)-4, (R,S p)-7 and 9 have been determined and are presented.

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DOI: S0022328X17303273