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Preparation and structural comparison of the ruthenium(0) derivatives Ru(DMPE)/sub 2/L (L = PMe/sub 3/, CO; DMPE = 1,2-bis(dimethylphosphino)ethane)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00231a016· OSTI ID:5582676
;
The thermal reaction of Ru(DMPE)/sub 2/(nap)H (DMPE = 1.2-bis(dimethylphosphino)ethane; nap = naphthyl) with PMe/sub 3/ results in the formation of the new zerovalent derivative Ru(DMPE)/sub 2/(PMe/sub 3/). The molecule crystallizes in orthorhombic space group Pnam with Z = 4 (d/sub calcd/ = 1.38 g/cm/sup 3/) and lattice parameters a = 16.3540 (18) A, b = 9.3240 (30) A, and c = 16.0210 (23) A. The structure displays a square-pyramidal geometry in which the PMe/sub 3/ occupies the apical position. Separate modeling of two disorders due to 4-fold rotation of the DMPE ligands about the apical Ru-P vector and 2-fold rotation of the PMe/sub 3/ ligand gives refinement to R/sub 1/ = 0.042, R/sub 2/ = 0.066. Some reactions of the low-valent derivative are reported. Displacement of PMe/sub 3/ by CO occurs at 25/sup 0/C, producing Ru(DMPE)/sub 2/(CO). Similarly, P(CD/sub 3/)/sub 3/ exchanges with coordinated PMe/sub 3/ more slowly. Neopentyl isocyanide slowly displaces PMe/sub 3/ at higher temperatures to give the isocyanide derivative. The CO adduct crystallizes in orthorhombic space group Pbca with Z = 16 and lattice parameters a = 19.110 (9) A, b = 23.116 (6) A, and c = 18.780 (6) A, the non-hydrogen atoms being refined to R/sub 1/ = 0.048, R/sub 2/ = 0.066. A trigonal-bipyramidal geometry is observed in which the CO occupies an equatorial site. The mechanism of substitution indicates both associative and dissociative pathways.
Research Organization:
Univ. of Rochester, NY
OSTI ID:
5582676
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

14 SOLAR ENERGY
140505 -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ADDUCTS
ALKANES
BOND ANGLE
BOND LENGTHS
CARBON COMPLEXES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DERIVATIZATION
DIMENSIONS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
LATTICE PARAMETERS
LENGTH
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPLEXES
PHOSPHINES
PHOSPHORUS COMPLEXES
PHOSPHORUS COMPOUNDS
RUTHENIUM COMPLEXES
SPACE GROUPS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VALENCE