Novel reactions of metal-metal bonds. Addition of sulfur dioxide and sulfur to Pd/sub 2/(Ph/sub 2/PCH/sub 2/PPh/sub 2/)/sub 2/Cl/sub 2/ and the oxidation of coordinated sulfide
Sulfur dioxide inserts into the metal-metal bond of Pd/sub 2/(dpm)/sub 2/X/sub 2/ (dpm = bis(diphenylphosphino)methane, X = Cl or Br), Pd/sub 2/(dam)/sub 2/Cl/sub 2/ (dam = bis(diphenylarsino)methane), and Pt/sub 2/(dpm)/sub 2/Cl/sub 2/. The adducts have been crystallized and characterized by infrared, electronic, and /sup 1/H NMR spectroscopy. The structure of Pd/sub 2/(dpm)/sub 2/(..mu..-SO/sub 2/)Cl/sub 2/ has been determined by x-ray crystallography. The compound crystallizes in the orthorhombic space group P2/sub 1/2/sub 1/2/sub 1/ with four molecules per unit cell of dimensions a = 15.582 (3), b = 16.457 (3), and c = 19.184 (5) A. Full-matrix least-squares refinement yields R = 0.069. The binuclear molecules contain two approximately planar palladium ions, each coordinated to a terminal chloride, a bridging sulfur dioxide, and two trans phosphorus donors from the bridging diphosphines. The ability of crystal packing forces to alter the Pd...Pd separation (3.383 (4) and 3.220 (4) A for the two crystallographically independent molecules) reflects the lack of a direct metal-metal bond. Pd/sub 2/(dpm)/sub 2/Cl/sub 2/ reacts with cyclo-octasulfur or propylene sulfide to give Pd/sub 2/(dpm)/sub 2/(..mu..-S)Cl/sub 2/, which has been crystallized and characterized by infrared, electronic, and /sup 1/H NMR spectra. Crystals of Pd/sub 2/(dpm)..mu..-S)Cl/sub 2/ are tetragonal, space group P4/sub 1/, with Z = 4 and cell dimensions a = 21.015 (4) and c = 14.281 (2) A. Refinement of this complex yields an R of 0.076. Oxidation of Pd/sub 2/(dpm)/sub 2/(..mu..-S)Cl/sub 2/ with m-chloroperbenzoic acid has been monitored by electronic spectroscopy at -60/sup 0/C; Pd/sub 2/(dpm)/sub 2/(..mu..-SO/sub 2/)Cl/sub 2/ is formed. The utility of the /sup 1/H NMR spectra of the methylene region of these dpm-bridged complexes in diagnosing the structure of the complexes is discussed. 5 figures, 8 tables.
- Research Organization:
- Univ. of California, Davis
- OSTI ID:
- 5549979
- Journal Information:
- Inorg. Chem.; (United States), Vol. 18:11, Issue 11
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PALLADIUM COMPLEXES
CHEMICAL BONDS
PLATINUM COMPLEXES
SULFUR
SULFUR DIOXIDE
CRYSTALLOGRAPHY
INFRARED SPECTRA
LOW TEMPERATURE
NUCLEAR MAGNETIC RESONANCE
OXIDATION
PALLADIUM COMPOUNDS
PLATINUM COMPOUNDS
STRUCTURAL CHEMICAL ANALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
ELEMENTS
MAGNETIC RESONANCE
NONMETALS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SPECTRA
SULFUR COMPOUNDS
SULFUR OXIDES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties