Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 849-850, Issue -, Pages 71-79Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2017.05.031
Keywords
Hydrogenation; Clusters; Ruthenium; Phosphirane
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Funding
- EPSRC [EP/G005206/1]
- Erasmus Mundus FFEEBB1 program office
- EPSRC [EP/G005206/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/G005206/1] Funding Source: researchfish
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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 [(mu-H)(4)Ru-4(CO)(11)((S)-1a)] (S)-2, [(mu-H)(4)Ru-4(CO)(11)((R)-1b)] (R)-3, 1,1-[(mu-H)(4)Ru-4(CO)(10)((S)-1c)] (S)-4, [(mu-H)(4)Ru-4(CO)(11)((S)-binaphthyl-P-(s)(H) Et)] (S, S-p)-5, [(mu-H)(4)Ru-4(CO)(11)((S)-binaphthyl-P-(R)(H) Et)] (S, R-p)-6, [(mu-H)(4)Ru-4(CO)(11)((R)-binaphthyl-P-(s)(H)Et)] (R,S-p)-7, [(mu-H)(4)Ru-4(CO)(11)((R)-binaphthyl-P-(R)(H)Et)] (R,R-p)-8 and the phosphinidene-capped triruthenium cluster [(mu-H)(2)Ru-3(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. (C) 2017 Elsevier B.V. All rights reserved.
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