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High nuclearity ruthenium carbonyl cluster chemistry IV1. Reactivity of [Ru10(μ-H)(μ6-C)(CO)24]-towards trimethylphosphite or bis(diphenylphosphino)acetylene; X-ray crystal structure of [PPh4][Ru10(μ-H)(μ6-C)22{P(OMe)3}2]

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/0022-328x(95)05896-w
  • Ruthenium
  • Carbonyl
  • Cluster
  • Crystal Structure


Abstract Reaction of [PPh 4][Ru 10( μ-H)( μ 6-C)(CO) 24] ( 1a) with two equivalents of trimenthylphosphite at room temperature gives a mixture of the mono- ( 2a), bis- ( 3a), tris- ( 4a) and tetrakis- ( 5a) phosphite-substituted cluster anions [Ru 10( μ-H)( μ 6-C)(CO) 24− x {P(OMe) 3} x] − ( x=1–4). Reaction of [Ru 2( μ-H)( μ-NC 5H 4) 2(CO) 4(NC 5H 5) 2] [Ru 10( μ-H)( μ 6-C)(CO) 24] ( 1b) with ten equivalents of trimethylphosphite at room temperature gives the tetrakis-substituted anion [Ru 10( μ-H)( μ 6-C)(CO) 20{P(OMe) 3} 4] as its [Ru 2( μ-H)( μ-NC 5H 4) 2(CO) 4{P(OMe 3} 2] + salt ( 5c). Cluster 3a has been characterized by an X-ray structural study, which confirms that the phosphite ligands occupy apical sites in these clusters. Reaction of [Ru 10( μ-H)( μ 6-C)(CO) 24] − with 20 equivalents trimethylphosphite in refluxing acetone leads to tetradecapping of the decaruthenium core and formation of Ru 6( μ- 6-C)(CO) 13{P(OMe 3} 4 ( 6). Reaction of 1b with 0.5 equivalents of bis(diphenylphosphino)acetylene gives the linked icosaruthenium cluster dianion [{ Ru 10(μ- H)(μ 6- C)( CO) 23} 2(μ- Ph 2 PC&.sbnpCPPh 2)] 2− ( 7b; heating 7b leads to loss of the phosphine rather than ligand-assisted condensation.

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