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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

Abdel-Magied, Ahmed F.; Majeed, Maitham H. LU ; Abelairas-Edesa, Manuel F.; Ficks, Arne; Ashour, Radwa M.; Rahaman, Ahibur LU ; Clegg, William; Haukka, Matti; Higham, Lee J. and Nordlander, Ebbe LU (2017) In Journal of Organometallic Chemistry
Abstract

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,... (More)

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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organization
publishing date
type
Contribution to journal
publication status
epub
subject
keywords
Clusters, Hydrogenation, Phosphirane, Ruthenium
in
Journal of Organometallic Chemistry
publisher
Elsevier
external identifiers
  • scopus:85020106466
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2017.05.031
language
English
LU publication?
yes
id
06c03307-ce4d-4dcd-8cfc-fc2ebf5c16ac
date added to LUP
2017-06-29 11:00:48
date last changed
2017-06-29 11:00:48
@article{06c03307-ce4d-4dcd-8cfc-fc2ebf5c16ac,
  abstract     = {<p>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)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>11</sub>((S)-1a)] (S)-2, [(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>11</sub>((R)-1b)] (R)-3, 1,1-[(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>10</sub>((S)-1c)] (S)-4, [(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>11</sub>((S)-binaphthyl-P<sub>(s)</sub>(H)Et)] (S,S <sub>p</sub>)-5, [(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>11</sub>((S)-binaphthyl-P<sub>(R)</sub>(H)Et)] (S,R <sub>p</sub>)-6, [(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>11</sub>((R)-binaphthyl-P<sub>(s)</sub>(H)Et)] (R,S <sub>p</sub>)-7, [(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>11</sub>((R)-binaphthyl-P<sub>(R)</sub>(H)Et)] (R,R <sub>p</sub>)-8 and the phosphinidene-capped triruthenium cluster [(μ-H)<sub>2</sub>Ru<sub>3</sub>(CO)<sub>9</sub>(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 <sub>p</sub>)-7 and 9 have been determined and are presented.</p>},
  author       = {Abdel-Magied, Ahmed F. and Majeed, Maitham H. and Abelairas-Edesa, Manuel F. and Ficks, Arne and Ashour, Radwa M. and Rahaman, Ahibur and Clegg, William and Haukka, Matti and Higham, Lee J. and Nordlander, Ebbe},
  issn         = {0022-328X},
  keyword      = {Clusters,Hydrogenation,Phosphirane,Ruthenium},
  language     = {eng},
  month        = {05},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Synthesis and characterization of chiral phosphirane derivatives of [(μ-H)<sub>4</sub>Ru<sub>4</sub>(CO)<sub>12</sub>] and their application in the hydrogenation of an α,β-unsaturated carboxylic acid},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2017.05.031},
  year         = {2017},
}