Hydrido thiolato and thiolato complexes of ruthenium(II) carbonyl phosphines. [cis,cis,trans-RuH(SR)(CO) sub 2 L sub 2 , cis,cis,trans-RuH(SR) sub 2 (CO) sub 2 L sub 2 where R = aryl and L = triphenylphosphine]
- Univ. of British Columbia, Vancouver (Canada)
Oxidative addition of RSH (R = H, alkyl, aryl) or RSSR (R = aryl) to Ru(CO){sub 2}L{sub 3} (L = PPh{sub 3}, 1) yields respectively cct-RuH(SR)(CO){sub 2L}{sub 2} (type 2) (cct = cis, cis, trans) or cct-Ru(SR){sub 2}(CO){sub 2}L{sub 2} (type 3); a hydrido selenolate species is made similarly using PhSeH. Methods for in situ formation of corresponding mixed bis(thiolate) species are also given. 1 is generally unreactive toward thioethers, although with propylene sulfide cct-Ru({eta}{sup 2}-S{sub 2}) (CO){sub 2}L{sub 2} is produced. Metathesis reaction of cct-RuCl{sub 2}(CO){sub 2}L{sub 2} with NaSR salts yield 3 (R = aryl) or, when R = Et, cct-RuCl(SEt)(CO){sub 2}L{sub 2} or (L(CO){sub 2}Ru({mu}{sub 3}-SEt)Na(THF)){sub 2} (4), depending on reaction conditions. The complexes are characterized by IR spectroscopy, {sup 1}H, {sup 31}P, and, in some cases, {sup 13}C NMR spectroscopy, and for 2g and 3g(R = SC{sub 6}H{sub 4}pMe) and 4, X-ray crystallography. All three complexes crystallized in the space group P {bar 1} 1. 4 has an unprecedented network of transition-metal and alkali-metal ions bridged by thiolate ligands: four thiolates bridge one Ru and one Na, and two thiolates bridge one Ru and two Na atoms. The geometries at Ru and Na are close to octahedral and square pyramidal respectively. Trends are noted for the {sup 1}H NMR shifts and {sup 2}J{sub PH} values for the hydride in 2, and an additivity rule formulated for the {sup 31}P shift within the cct-Ru(SR)(SR')(CO){sub 2}(PPh{sub 3}){sub 2} species. Limited kinetic data suggest that the oxidative addition reactions to 1 probably proceed via a nonradical process, following dissociation of a PPh{sub 3} ligand.
- OSTI ID:
- 7273935
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:24; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BOND ANGLE
BOND LENGTHS
CARBON 13
CARBON ISOTOPES
CARBONYLS
CATALYSTS
CATIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL SHIFT
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DESULFURIZATION
DIFFRACTION
DIMENSIONS
DISSOCIATION
EVEN-ODD NUCLEI
FUELS
INFRARED SPECTRA
IONS
ISOTOPES
KINETICS
LENGTH
LIGANDS
LIGHT NUCLEI
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
PHOSPHINES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
REACTION KINETICS
RUTHENIUM COMPLEXES
SCATTERING
SPECTRA
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
THIOLS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION