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Cluster framework rearrangements. An unusual transformation of a butterfly cluster into a rhombus. The crystal and molecular structures of Os/sub 4/(CO)/sub 12/(. mu. /sub 3/-S)(. mu. -HC/sub 2/R), R = Ph and CO/sub 2/Me

Conference · · J. Am. Chem. Soc.; (United States)
OSTI ID:6613730
;
The ability of transition-metal cluster compounds to undergo structural transformations of their metal frameworks has been shown to play an intimate and important role in their chemistry. Most frequently these transformations are induced by ligand additions or eliminations, but they can also be induced by ligand transformations. Some recent reports have been described unusual examples of dynamically rapid degenerate rearrangements. In their recent studies they have observed the formation of the unusual butterfly cluster complexes Os/sub 4/(CO)/sub 12/(..mu../sub 4/-eta/sup 3/-SC(R)=CH) (1a, b R = Ph, CO/sub 2/Me) by the insertion of terminal alkynes into a metal-sulfur bond in the cluster compound Os/sub 4/(CO)/sub 12/(..mu../sub 3/-S). When refluxed in octane solvent, these compounds are decarbonlated and are transformed into the new complexes Os/sub 4/-(CO)/sub 11/(..mu../sub 4/-S)(..mu../sub 4/-HC/sub 2/R) (4a, b, R = Ph, CO/sub 2/Me) that contain a rhombohedral arrangement of metal atoms with quadruply bridging sulfido and alkyne ligands on opposite sides of the cluster. They have now isolated and characterized two intermediates that show in great detail a remarkable rearrangement of the metal atom framework that has accompanied the transformation of 1 into 4.
Research Organization:
Univ. of South Carolina, Columbia
OSTI ID:
6613730
Conference Information:
Journal Name: J. Am. Chem. Soc.; (United States) Journal Volume: 109:3
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
CARBONYLS
CHEMICAL BONDS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
OSMIUM COMPLEXES
PHOSPHINES
PHOSPHORUS COMPOUNDS
SULFUR COMPLEXES
TRANSITION ELEMENT COMPLEXES