Substitution reactions of a μ3121-C60 triosmium cluster complex and formation of a novel μ3121-C60 bonding mode

Hyunjoon Song, Jae Ik Choi, Kwangyeol Lee, Moon Gun Choi, Joon T. Park

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Decarbonylation of Os3(CO)8(CNR)(μ3-CNR)(μ3121-C60) (1; R = CH2Ph) with Me3NO/ MeCN and subsequent thermal reactions with various 2e-donor ligands afford the respective substitution products Os3(CO)7(CNR)(μ3-CNR)(L)(C60) (L = (μ-H)2 (2), CNR (3), PMe3 (4), PPh3 (5)) in high yields. Compounds 2-5 have been characterized by spectroscopic (MS, IR, and 1H, 13C, and 31P NMR) and microanalytical data. Compounds 3 and 4 consist of three isomeric forms due to a 3-fold rotation on the outer Os center with a terminal benzyl isocyanide ligand, whereas 2 and 5 exist as a single isomer. The molecular structures of 2-5 have been determined by X-ray single-crystal diffraction studies. The hydride ligands of 2 have not been directly located, but ligand arrangements around the inner Os atom of the open-chain Os3 framework suggest that the two hydride ligands bridge the two Os-Os edges, respectively. The added isocyanide ligand in 3 is coordinated to an equatorial site on the inner Os center. The PMe3 ligand in 4 is positioned at the axial site of the inner Os atom. The μ3121-C60 interactions between C60 and metal clusters are not significantly altered by substitution of the corresponding ligands in 2-4. The PPh3 ligand in 5, however, is bound at the less hindered equatorial site of the outer Os center and leads to an orbital reorganization of the C6 ring of C60 from μ3121-C60 (1) to μ3112-C60 (5).

Original languageEnglish
Pages (from-to)5221-5228
Number of pages8
JournalOrganometallics
Volume21
Issue number24
DOIs
Publication statusPublished - 2002 Nov 25
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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