Cluster synthesis. 2. The role of heteroatoms in the formation of high nuclearity transition-metal carbonyl cluster compounds. The condensation of small clusters
The compounds HOs/sub 3/(..mu../sub 3/-S)(..mu..-HC double bond NR)(CO)/sub 9/, Ia, R = C/sub 6/H/sub 5/, and Ia', R = C/sub 6/H/sub 4/-p-F, lose CO and/or H/sub 2/ when heated to form the hexanuclear osmium complexes Os/sub 6/(..mu../sub 4/-S)(..mu..-HC double bond NR)/sub 2/(CO)/sub 18/, IIa, R = C/sub 6/H/sub 5/, and IIa', R = C/sub 6/H/sub 4/-p-F, H/sub 2/Os/sub 6/(..mu../sub 4/-S)(..mu../sub 3/-S)(..mu..-HC double bond NR)/sub 2/(CO)/sub 17/, IIIa,b, R = C/sub 6/H/sub 5/, and IIIa',b', R = C/sub 6/H/sub 4/-p-F, which exist as two isomers, H/sub 2/Os/sub 6/(..mu../sub 4/-S)(..mu../sub 3/-S)(..mu..-HC double bond NR)/sub 2/(CO)/sub 16/, IVa-c, R = C/sub 6/H/sub 5/, and IVa'-c', R = C/sub 6/H/sub 4/-p-F, which exist as three isomers, and Os/sub 6/(..mu../sub 4/-S)/sub 2/(..mu..-HC double bond NR)/sub 2/(CO)/sub 15/, Va, R = C/sub 6/H/sub 5/, and Va', R = C/sub 6/H/sub 4/-p-F. All compounds have been analyzed by ir and /sub 1/H NMR spectroscopy. Compounds IIIa', IVa and Va have also been characterized by single-crystal x-ray diffraction analyses. Compounds III can be converted to IV, and IV into V. III, IV, and V are believed to be part of a sequence of cluster growth processes in which the sulfido ligands mediate the initial linking of the clusters and the subsequent formation of metal-metal bonds between them. IIIa' contains two open triangular groups of three metal atoms linked by a tetrahedrally coordinated sulfido ligand. In IVa the six metal atoms are arranged in groups of four and two, with the two groups linked by a tetrahedrally coordinated sulfido ligand. In Va the six metal atoms have condensed into a central cluster of four which has the form of a butterfly tetrahedron with sulfido ligands bridging the two open triangular faces. The two remaining metal atoms are bonded to the hinge metal atoms of the central cluster, one to each.
- Research Organization:
- Yale Univ., New Haven, CT
- DOE Contract Number:
- AC02-78ER04900
- OSTI ID:
- 6165160
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 105:4
- Country of Publication:
- United States
- Language:
- English
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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
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)
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
OSMIUM COMPOUNDS
EXPERIMENTAL DATA
INFRARED SPECTRA
NUCLEAR MAGNETIC RESONANCE
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
COHERENT SCATTERING
DATA
DIFFRACTION
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
RESONANCE
SCATTERING
SPECTRA
SYNTHESIS
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)