Mixed transition metal-main group atom clusters as potential models for M[sub x]X (010) and M[sub 4] (100) surfaces. Synthesis and spectroscopic and structural characterization of M[sub 4](CO)[sub 13]([mu][sub 3]-PPh) (M = Ru, Os). Pyramidal clusters with M[sub 3]P square faces
- Univ. of Waterloo, Ontario (Canada)
The clusters HM[sub 3](CO)[sub 10]([mu]-PPh[sub 2]) (M = Ru (1a), Os (1b)) are shown to be convenient precursors of the phosphinidene-stabilized clusters nido-M[sub 4](CO)[sub 13]([mu][sub 3]-PPh) (M = Ru (2a), Os (2b)) via P-C(Ph) activation, reductive elimination of benzene, and condensation. Heating a toluene solution of 1a under a purge of carbon monoxide forms Ru[sub 4](CO)[sub 13]([mu][sub 3]-PPh) (40%) as the major product. Formation of Os[sub 4](CO)[sub 13]([mu][sub 3]-PPh) requires more forcing conditions. Heating a solid sample of 1b at 215[degrees]C for 8 min affords 2b in 20-25% yield. Both 2a and 2 b have been characterized by spectroscopy and by accurate single-crystal X-ray structure analyses. Crystals of 2a and 2b are isomorphous, crystallizing in the orthorhombic space group P2[sub 1]2[sub 1]2[sub 1]. The molecular structures of 2a and 2b possess M[sub 4]P cluster frameworks containing a butterfly arrangement of metal atoms stabilized by a [mu][sub 3]-phosphinidene fragment capping an open triangular face. Both clusters adhere to the effective atomic number rule (62 electrons) and are associated with nido octahedral M[sub 4]P core geometries when the skeletal bonding electrons are considered (seven skeletal electron pairs, five vertices). In the latter instance the [open quotes]PPh[close quotes] fragment is located in the square basal plane of the pyramidal framework. Variable-temperature [sup 13]C NMR studies of 2a revealed four independent dynamic processes involving localized CO exchange, and a direct comparison is drawn between 2a and ([mu]-H)[sub 2]Ru[sub 4](CO)[sub 12]([mu][sub 3]-PPh). At temperatures in excess of 296 K, the authors have observed the onset of total intermetallic CO scrambling. 47 refs., 5 figs., 4 tabs.
- OSTI ID:
- 6046914
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:9; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
OSMIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
RUTHENIUM COMPLEXES
CARBONYLS
CHEMICAL REACTION YIELD
CRYSTAL STRUCTURE
ELECTRON PAIRS
LATTICE PARAMETERS
MILLER INDICES
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
ORTHORHOMBIC LATTICES
PHOSPHORUS COMPOUNDS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
MAGNETIC RESONANCE
RESONANCE
SCATTERING
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties