Trichloro-bridged diruthenium(II,III) complexes: preparation, properties, and X-ray structure of Ru/sub 2/Cl/sub 5/(chiraphos)/sub 2/ (chiraphos = 2(S),3(S)-bis(diphenylphosphino)butane)
The triply chloro-bridged, formally mixed-valence compounds (RuCl(P-P))/sub 2/(..mu..-Cl)/sub 3/ have been prepared by phosphine exchange from Ru(III) precursors containing PPh/sub 3/ or P(p-tolyl)/sub 3/ (P-P: chirphos, 2(S),3(S)-bis(diphenylphosphino)butane;PPh/sub 2/(CH/sub 2/)/sub n/PPh/sub 2/, n = 3 or 4; diop, 4(s),5(S)-bis((diphenylphosphino)methyl)-2,2-dimethyl-1,3-dioxolane). The chiraphos complex 1 has been characterized by X-ray analysis and is a highly symmetrical (..mu..-Cl)/sub 3/ species with irregular octahedral geometry about each Ru (space group P1; a = 11.826 (2) A, b = 11.968 (1) A, c = 12.075 (2) A, ..cap alpha.. = 112.333 (6)/sup 0/, ..beta.. = 92.409 (9)/sup 0/, ..gamma.. = 103.006 (7)/sup 0/; Z = 1; the structure was refined to a conventional R value of 0.035 by using 6782 significant reflections and 405 variables). The crystallography data for 1, and near-infrared spectral data in a range of solvents, show the dimers to be valence-delocalized. The complexes undergo disproportionation rapidly in CH/sub 3/CN and more slowly in Me/sub 2/SO and CH/sub 3/NO/sub 2/ to give dimeric Ru/sub 2//sup III/ and Ru/sub 2//sup II/ species. In CCl/sub 4/ or toluene, 1 exists in some other valence-delocalized form, possibly as a tetranuclear cluster. 35 references, 6 figures, 1 table.
- Research Organization:
- Univ. of British Columbia, Vancouver
- OSTI ID:
- 6036795
- Journal Information:
- Inorg. Chem.; (United States), Vol. 25:2
- Country of Publication:
- United States
- Language:
- English
Similar Records
Mono- and bis(bis(diphenylphosphino)methane)-bridged Ru-Rh complexes. Preparation, characterization, and reactivity. X-ray crystal structure of RuRhH(Ph)(PhPCH/sub 2/PPh/sub 2/)(Ph/sub 2/PCH/sub 2/PPh/sub 2/)(C/sub 8/H/sub 12/) x 1/2PhMe and of RuHCl(Ph/sub 2/PCH/sub 2/PPh/sub 2/)/sub 2/ x 1/2PhMe
Heterodifunctional ligands derived from monooxidized Bis(phosphino)amines. Synthesis and transition metal (Molybdenum(0), Tungsten(0), Rhodium(I), Palladium(II), and Platinum(II)) complexes of (Diphenylphosphino)(diphenylphosphinothioyl)- and (Diphenylphosphino) (diphenylphosphinoselenoyl)phenylamine, Ph[sub 2]PN(Ph)P(E)PH[sub 2] (E = S, Se). Crystal and molecular structure of the Pt(II) Complex [Cl[sub 2]P[ovr tPPh[sub 2]N(Ph)P(S)]Ph[sub 2]][center dot]H[sub 2]O
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
14 SOLAR ENERGY
CHLORINE COMPOUNDS
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
ORGANIC COMPOUNDS
PHOSPHINES
RUTHENIUM COMPOUNDS
DIMERS
EXPERIMENTAL DATA
INFRARED SPECTRA
LATTICE PARAMETERS
SPACE GROUPS
VALENCE
X-RAY DIFFRACTION
COHERENT SCATTERING
DATA
DIFFRACTION
HALOGEN COMPOUNDS
INFORMATION
NUMERICAL DATA
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
SCATTERING
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
140505 - Solar Energy Conversion- Photochemical
Photobiological
& Thermochemical Conversion- (1980-)