Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S)

Adams, R D; Chen, Gong; Sun, Sixiu; Tanner, J T; Wolfe, T A

doi:10.1021/om00115a037

Cluster complexes containing ynamine ligands. 1. Synthesis and structural characterizations of the complexes Os sub 4 (CO) sub 11 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(Me)C(NMe sub 2 )C(NMe sub 2 )CMe)(. mu. sub 3 -S), Os sub 4 (CO) sub 11 (. mu. -C(NMe sub 2 )C(Me)C(Me)C(NMe sub 2 ))(. mu. sub 3 -S), Os sub 4 (CO) sub 9 (. mu. -MeC sub 2 NMe sub 2 )(. mu. -C(Me)C(NMe sub 2 )C(Me)C(NMe sub 2 ))-(. mu. sub 3 -S), and Os sub 3 (CO) sub 7 (. mu. sub 3 -MeC sub 2 NMe sub 2 )(. mu. -MeC sub 2 NMe sub 2 )(. mu. sub 3 -S)

Journal Article · Sun Dec 31 23:00:00 EST 1989 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00115a037· OSTI ID:6654526

Adams, R D; Chen, Gong; Sun, Sixiu; Tanner, J T; Wolfe, T A ^[1]

Univ. of South Carolina, Columbia (USA)

The reaction of Os{sub 4}(CO){sub 12}({mu}{sub 3}-S) (1) with MeC{sub 2}NMe{sub 2} yielded the complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (2), Os{sub 4}(CO){sub 11}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (3), Os{sub 4}(CO){sub 11}({mu}-C(Me)C(NMe{sub 2})C(NMe{sub 2})CMe)({mu}{sub 3}-S) (4), Os{sub 4}(CO){sub 11}({mu}-C(NMe{sub 2})C(Me)C(Me)C(NMe{sub 2}))({mu}{sub 3}-S) (5), Os{sub 4}(CO){sub 9}({mu}-MeC{sub 2}NMe{sub 2})({mu}-C(Me)C(NMe{sub 2})C(Me)C(NMe{sub 2}))({mu}{sub 3}-S) (6), and Os{sub 3}(CO){sub 7}({mu}{sub 3}-MeC{sub 2}NMe{sub 2})({mu}-MeC{sub 2}NMe{sub 2})({mu}{sub 3}-S) (7), all in low yields. Compounds 3-7 are new and have been characterized by Ir, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. Compound 3 contains a chain of four osmium atoms with two bridging ynamine ligands and a bridging sulfido ligand. Both ynamine ligands contain strong {pi}-bonding interactions between the NMe{sub 2} groups and the neighboring carbon atom in the alkynyl groups. These interactions alter the metal-carbon bonding, and the ynamine ligands adopt structures that resemble aminocarbene ligands. Similar structures were found for the ynamine ligands in 7. Compounds 4-6 contain spiked triangular clusters of four osmium atoms with a triply bridging sulfido ligand on the triangular grouping. Each of these compounds also contains a metallacyclopentadiene group formed by the coupling of two ynamine ligands. In each compound, the two ynamine ligands have been coupled in a different way. In 4, they were coupled tail to tail. In 5 they were coupled head to head, and in 6 they were coupled head to tail. There is structural evidence for significant, albeit weaker, {pi}-bonding interactions between the amino groups and the adjacent carbon atoms in these complexes. This seems to produce a weakening of the corresponding metal-carbon bonding.

OSTI ID:: 6654526

Journal Information:: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:1; ISSN 0276-7333; ISSN ORGND

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200* -- Inorganic
Organic
& Physical Chemistry
CLUSTER MODEL
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MATHEMATICAL MODELS
MEASURING INSTRUMENTS
MEASURING METHODS
NUCLEAR MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES

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