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Title: 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]

Abstract

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 tomore » 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.« less

Authors:
; ; ;  [1]
  1. Univ. of British Columbia, Vancouver (Canada)
Publication Date:
OSTI Identifier:
7273935
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 30:24; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 01 COAL, LIGNITE, AND PEAT; RUTHENIUM COMPLEXES; CHEMICAL PREPARATION; STRUCTURAL CHEMICAL ANALYSIS; BOND ANGLE; BOND LENGTHS; CARBON 13; CARBONYLS; CATALYSTS; CATIONS; CHEMICAL REACTION KINETICS; CHEMICAL SHIFT; CRYSTAL STRUCTURE; DESULFURIZATION; DISSOCIATION; FUELS; INFRARED SPECTRA; LIGANDS; MOLECULAR STRUCTURE; NMR SPECTRA; OXIDATION; PHOSPHINES; PHOSPHORUS 31; THIOLS; X-RAY DIFFRACTION; CARBON ISOTOPES; CHARGED PARTICLES; CHEMICAL REACTIONS; COHERENT SCATTERING; COMPLEXES; DIFFRACTION; DIMENSIONS; EVEN-ODD NUCLEI; IONS; ISOTOPES; KINETICS; LENGTH; LIGHT NUCLEI; NUCLEI; ODD-EVEN NUCLEI; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PHOSPHORUS COMPOUNDS; PHOSPHORUS ISOTOPES; REACTION KINETICS; SCATTERING; SPECTRA; STABLE ISOTOPES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 010402 - Coal, Lignite, & Peat- Purification & Upgrading

Citation Formats

Jessop, P G, Rettig, S J, Lee, Chungli, and James, B R. 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]. United States: N. p., 1991. Web. doi:10.1021/ic00024a031.
Jessop, P G, Rettig, S J, Lee, Chungli, & James, B R. 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]. United States. https://doi.org/10.1021/ic00024a031
Jessop, P G, Rettig, S J, Lee, Chungli, and James, B R. 1991. "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]". United States. https://doi.org/10.1021/ic00024a031.
@article{osti_7273935,
title = {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]},
author = {Jessop, P G and Rettig, S J and Lee, Chungli and James, B R},
abstractNote = {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.},
doi = {10.1021/ic00024a031},
url = {https://www.osti.gov/biblio/7273935}, journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 30:24,
place = {United States},
year = {Wed Nov 27 00:00:00 EST 1991},
month = {Wed Nov 27 00:00:00 EST 1991}
}