Binuclear rhodium complexes: their chemistry with sulfur dioxide and the structure of (Rh/sub 2/Cl/sub 2/(. mu. -SO/sub 2/)((C/sub 6/H/sub 5/)/sub 2/PCH/sub 2/P(C/sub 6/H/sub 5/)/sub 2/)/sub 2/)
Journal Article
·
· Inorg. Chem.; (United States)
The A-frame complex (Rh/sub 2/(CO)/sub 2/(..mu..-Cl)(DPM)/sub 2/)(B(C/sub 6/H/sub 5/)/sub 4/) (DPM = (C/sub 6/H/sub 5/)/sub 2/PCH/sub 2/P(C/sub 6/H/sub 5/)/sub 2/) undergoes a facile and reversible reaction with SO/sub 2/ to yield (Rh/sub 2/(CO)/sub 2/(..mu..-Cl)(..mu..-SO/sub 2/)(DPM)/sub 2/)(B(C/sub 6/H/sub 5/)/sub 4/). Spectroscopic studies have shown that SO/sub 2/ attack occurs directly at the bridging site of the A-frame complex. Treatment of a solution of the SO/sub 2/ adduct with excess SO/sub 2/ in the presence of chloride ion yields a second SO/sub 2/ complex, (Rh/sub 2/Cl/sub 2/(..mu..-SO/sub 2/)(DPM)/sub 2/), the structure of which is reported. In the absence of chloride ion, formation of the second SO/sub 2/ complex occurs in the presence of small amounts of (RhCl/sub 2/(CO)/sub 2/)/sup -/ with the latter functioning as a chloride-transfer agent. Treatment of the second, SO/sub 2/-bridged species with CO yields the complex (Rh/sub 2/(CO)/sub 2/(..mu..-CO)(..mu..-Cl)(DPM)/sub 2/)(Cl) which can then be readily converted in solution to the dicarbonyl species cis-(Rh/sub 2/Cl/sub 2/(CO)/sub 2/(DPM)/sub 2/). The reaction of trans-(Rh/sub 2/Cl/sub 2/(CO)/sub 2/(DPM)/sub 2/) with SO/sub 2/ has also been investigated and has been shown to occur by terminal SO/sub 2/ attack, forcing the terminal carbonyl and chloro ligands on one Rh atom into the bridging positions. In solution this species then loses Cl/sup -/ and rearranges to the complex (Rh/sub 2/(CO)/sub 2/(..mu..-Cl)(..mu..-SO/sub 2/)(DPM)/sub 2/)(Cl) which can yield (Rh/sub 2/Cl/sub 2/(..mu..-SO/sub 2/)(DPM)/sub 2/) by recoordination of Cl/sup -/ and subsequent CO loss. The x-ray structural determination of (Rh/sub 2/Cl/sub 2/(..mu..-SO/sub 2/)(DPM)/sub 2/) shows this species to be a distorted A-frame complex with a symmetrical bridging SO/sub 2/ ligand and terminal chloro ligands.
- Research Organization:
- Univ. of Alberta, Edmonton
- OSTI ID:
- 5102652
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:1; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACTIVATION ENERGY
ADDUCTS
AROMATICS
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DATA
DIMENSIONS
ENERGY
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
LATTICE PARAMETERS
LEAST SQUARE FIT
LENGTH
MAGNETIC RESONANCE
MAXIMUM-LIKELIHOOD FIT
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
RHODIUM COMPLEXES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACTIVATION ENERGY
ADDUCTS
AROMATICS
BOND ANGLE
BOND LENGTHS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DATA
DIMENSIONS
ENERGY
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
LATTICE PARAMETERS
LEAST SQUARE FIT
LENGTH
MAGNETIC RESONANCE
MAXIMUM-LIKELIHOOD FIT
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
RHODIUM COMPLEXES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES
TRANSITION ELEMENT COMPLEXES
YIELDS