Mixed platinum-rhodium carbonyl clusters. Synthesis, reactivity, and chemical characterization of the (PtRh/sub 8/(. mu. /sub 3/-CO)/sub 3/(. mu. -CO)/sub 9/(CO)/sub 7/)/sup 2 -/ anion and X-ray crystal structure of its tetraethylammonium salt
The anion (PtRh/sub 8/(CO)/sub 19/)/sup 2 -/ has been synthesized by reaction of (PtRh/sub 4/(CO)/sub 12/)/sup 2 -/ with Rh/sub 4/(CO)/sub 12/. It shows considerable reactivity toward CO, from which it is readily decomposed. The structure of the dianion has been determined by X-ray analysis of the tetraethylammonium salt. Crystal data: C/sub 35/H/sub 40/N/sub 2/O/sub 19/PtRh/sub 8/, M/sub r/ = 1811.0, orthorhombic, space group Pmnb (nonstandard setting of Pnma (No. 62)), a = 12.338 (3) A, b = 16.340 (3) A, c = 24.385 (8) A, Z = 4; final R = 0.039, R/sub w/ = 0.052. The anion, of crystallographic C/sub s/ symmetry, shows a metallic skeleton that can be described as a stack of three triangles, generating two face-to-face condensed octahedra (the Pt atom being in the central triangle, in one of the positions of highest M-M connectivity); seven carbonyls, out of nineteen, are terminal, nine edge-bridging and three face-bridging. Variable-temperature /sup 13/C NMR spectra show at room temperature complete scrambling of the carbonyls over the metallic frame with simultaneous coupling with all Rh and Pt atoms. At -100/sup 0/C a still partially dynamic situation is observed, which yields an ill-defined spectrum. 13 references, 3 figures, 2 tables.
- Research Organization:
- CNR, Milano, Italy
- OSTI ID:
- 5905087
- Journal Information:
- Inorg. Chem.; (United States), Vol. 25:5
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM COMPOUNDS
CRYSTAL STRUCTURE
CARBONYLS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
PLATINUM
RHODIUM
ANIONS
BOND ANGLE
BOND LENGTHS
CARBON MONOXIDE
EXPERIMENTAL DATA
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
SALTS
SPACE GROUPS
X-RAY DIFFRACTION
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHARGED PARTICLES
COHERENT SCATTERING
DATA
DIFFRACTION
DIMENSIONS
ELEMENTS
INFORMATION
IONS
LENGTH
MAGNETIC RESONANCE
METALS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PLATINUM METALS
RESONANCE
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENTS
400201* - Chemical & Physicochemical Properties