Fluxional processes and structural characterization of mu(3)-eta(2),eta(2),eta(2)-C-60 triosmium cluster complexes, Os-3(CO)(9-n)(PMe3)(n)(mu(3)-eta(2),eta(2),eta(2)-C-60) (n=1, 2, 3)

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The title complex, Os-3(CO)(6)(PMe3)(3)(mu(3)-eta(2),eta(2),eta(2)-C-60) (3), has been prepared by decarbonylation of Os-3(CO)(9)(mu(3)-eta(2),eta(2),eta(2)-C-60) with three equivalents of Me3NO in the presence of excess PMe3 ligand. The solid-state structures of Os-3(CO)(7)(PMe3)(2)(mu(3)-eta(2),eta(2),eta(2)-C-60) (2) and 3 have been determined by single-crystal X-ray diffraction studies. Compound 2 has two inequivalent equatorial phosphine ligands on adjacent osmium atoms and compound 3, with a distorted C-3 symmetry, has one equivalent equatorial phosphine ligand on each osmium center. The fluxional processes of Os-3(CO)(8)(PMe3)(mu(3)-eta(2),eta(2),eta(2)-C-60) (1), 2 and 3 have been examined by variable-temperature C-13- and P-31-NMR studies. Only one isomer exists in solution and a restricted ligand rotation on each phosphine-substituted osmium center appears to occur for all three compounds, 1-3. Activation barriers for the carbonyl exchange process increase with increasing phosphine substitution, presumably, due to the steric effect of the phosphine ligands. (C) 2000 Elsevier Science S.A. All rights reserved.
Publisher
ELSEVIER SCIENCE SA
Issue Date
2000-04
Language
English
Article Type
Article
Keywords

LIGAND-SUBSTITUTED DERIVATIVES; X-RAY STRUCTURES; C-60; FULLERENES; OS3(CO)12; STEREOCHEMISTRY; PENTARUTHENIUM; COORDINATION; P(OCH2CF3)3; CHEMISTRY

Citation

JOURNAL OF ORGANOMETALLIC CHEMISTRY, v.599, no.1, pp.49 - 56

ISSN
0022-328X
URI
http://hdl.handle.net/10203/20019
Appears in Collection
CH-Journal Papers(저널논문)
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