Cluster condensation reactions. Transformation of two triangular trinuclear clusters into a hexanuclear cluster containing a novel edge-fused bitetrahedral structure
The carbene-containing cluster complex Os/sub 3/(CO)/sub 9/(C(H)NMe/sub 2/)..mu..-SMe)(..mu..-H) (1) was prepared in 56% yield from the reaction of Os/sub 3/(CO)/sub 10/(..mu..-SMe)(..mu..-H) with CH/sub 2/(NMe/sub 2/)/sub 2/. UV irradiation of 1 yielded the complex Os/sub 3/(CO)/sub 8/(..mu..-CNMe/sub 2/)(..mu..-SMe)(..mu..-H)/sub 2/ (2) in 68% yield. Compound 2 contains a bridging (dimethylamino)carbyne ligand that was formed by an ..cap alpha..-CH activation of the carbene ligand in 1. Thermal decarbonylation of 2 resulted in the formation of the hexaosmium cluster complex Os/sub 6/-(CO)/sub 12/(..mu..-CNMe/sub 2/)/sub 2/(..mu..-SMe)/sub 2/(..mu..-H)/sub 2/ (3) in 65% yield. Compound 3 was characterized by a single-crystal X-ray diffraction analysis. The structure was solved by a combination of direct methods and difference Fourier techniques and was refined (2701 reflections) to the final values of the residuals R = 0.048 and R/sub w/ = 0.050. The structure consists of six osmium atoms arranged in the form of two tetrahedral clusters that have one edge in common. There are two bridging (dimethylamino)carbyne ligands and two triply bridging methanethiolato ligands that appear to serve as three-electron donors instead of the usual five-electron-donor configuration. 18 references, 3 figures, 4 tables.
- Research Organization:
- Univ. of South Carolina, Columbia
- OSTI ID:
- 6450586
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:7; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Clusters containing carbene ligands. 3. The transformations of a (dimethylamino)methyl ligand in a triosmium cluster. The synthesis and structural characterizations of Os/sub 3/(CO)/sub 10/(. mu. -eta/sup 2/-H/sub 2/CNMe/sub 2/)(. mu. -H), Os/sub 3/(CO)/sub 9/(. mu. /sub 3/-eta/sup 2/-C(H)NMe/sub 2/)(. mu. -H)/sub 2/, and Os/sub 3/(CO)/sub 10/(. mu. -CNMe/sub 2/)(. mu. -H)
Clusters containing carbene ligands. Novel example of carbene ligand transfer from a metal atom to a carbon atom
Related Subjects
400201* -- Chemical & Physicochemical Properties
CARBONYLS
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EXPERIMENTAL DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OSMIUM COMPLEXES
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION