Synthesis and coordination of stibine and bismuthine ligands with transition metals
Synthesis and coordination of stibine and bismuthine ligands with transition metals
The complexes trans[RuX2L4] (X = Cl, Br, I; L = AsMe2Ph, SbMe2Ph) and trans-[RuX2(L-L)2] (X = Cl, Br, I; L-L = Ph2Sb(CH2)3SbPh2) have been prepared from RuCl3.nH2O, LiX and L and from [Ru(dmf)6][CF3SO3]3 (dmf = dimethylformamide), LiX and L or L-L. Oxidation of trans-[RuX2L4] and trans-[RuX2(L-L)2] to trans[RuX2L4][BF4] and trans-[RuX2(L-L)2][BF4] has been achieved either using AgBF4 in CH2Cl2 or concentrated HNO3 in aqueous HBF4. The complexes have been characterised by analysis, UV-Vis, IR and 1H NMR spectroscopy and the RuII -RuIII oxidations probed by cyclic voltammetry.
Complexes of the distibinomethane ligands, Ph2SbCH2SbPh2 (dpsm) or Me2SbCH2SbMe2 (dmsm) with copper, silver, gold, platinum, palladium, rhodium, ruthenium and osmium have been prepared. Complexes have been characterised by analysis, mass spectrometry and multinuclear NMR (1H, 13C,{1H}, 63Cu, 109Ag and 195Pt). The single crystal structures of cis, trans-[{PtCl2(dpsm)}2], cis, trans-[{PtBr2(dpsm)}2] and cis, trans-[{PdBr2(dpsm)}2] have been determined and show unique geometries. Single crystal structures of trans, trans-[{PdI2(dpsm)}2] and [RuI2(dpsm)3] have also been determined the last being the first reported example of dpsm acting as a chelate.
Complexes of triphenylantimony and the distibinomethane ligands with manganese and rhenium carbonyls and carbonyl halides have been prepared for [Mn2(CO)10], [Re2(CO)10], [Mn(CO)5Cl] and [Re(CO)5Cl]. The single crystal X-ray structures of ax-[Mn2(CO)9(SbPh3)], [Mn2(CO)6(dpsm)2], [Mn(CO)5(SbPh3)][CR3SO3] and fac-[Re(CO)3Cl(SbPh3)2] have also been obtained.
Substituted group 6 carbonyl complexes of the distibinomethane ligands of types [M(CO)5(η1dpsm)], [(OC)4M(μ-dpsm)2M(CO)4] and [(OC)4M(μ-dmsm)2M(CO)4] (M = Cr, Mo, W) have been prepared. The single crystal structures of all tungsten complexes have also been obtained. The effect of coordination on the C-Sb-C angles and the Sb-C lengths in dpsm and SbPh3 has also been examined using the Cambridge Structural Database (CSD).
University of Southampton
1999
Holmes, Nicholas James
(1999)
Synthesis and coordination of stibine and bismuthine ligands with transition metals.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The complexes trans[RuX2L4] (X = Cl, Br, I; L = AsMe2Ph, SbMe2Ph) and trans-[RuX2(L-L)2] (X = Cl, Br, I; L-L = Ph2Sb(CH2)3SbPh2) have been prepared from RuCl3.nH2O, LiX and L and from [Ru(dmf)6][CF3SO3]3 (dmf = dimethylformamide), LiX and L or L-L. Oxidation of trans-[RuX2L4] and trans-[RuX2(L-L)2] to trans[RuX2L4][BF4] and trans-[RuX2(L-L)2][BF4] has been achieved either using AgBF4 in CH2Cl2 or concentrated HNO3 in aqueous HBF4. The complexes have been characterised by analysis, UV-Vis, IR and 1H NMR spectroscopy and the RuII -RuIII oxidations probed by cyclic voltammetry.
Complexes of the distibinomethane ligands, Ph2SbCH2SbPh2 (dpsm) or Me2SbCH2SbMe2 (dmsm) with copper, silver, gold, platinum, palladium, rhodium, ruthenium and osmium have been prepared. Complexes have been characterised by analysis, mass spectrometry and multinuclear NMR (1H, 13C,{1H}, 63Cu, 109Ag and 195Pt). The single crystal structures of cis, trans-[{PtCl2(dpsm)}2], cis, trans-[{PtBr2(dpsm)}2] and cis, trans-[{PdBr2(dpsm)}2] have been determined and show unique geometries. Single crystal structures of trans, trans-[{PdI2(dpsm)}2] and [RuI2(dpsm)3] have also been determined the last being the first reported example of dpsm acting as a chelate.
Complexes of triphenylantimony and the distibinomethane ligands with manganese and rhenium carbonyls and carbonyl halides have been prepared for [Mn2(CO)10], [Re2(CO)10], [Mn(CO)5Cl] and [Re(CO)5Cl]. The single crystal X-ray structures of ax-[Mn2(CO)9(SbPh3)], [Mn2(CO)6(dpsm)2], [Mn(CO)5(SbPh3)][CR3SO3] and fac-[Re(CO)3Cl(SbPh3)2] have also been obtained.
Substituted group 6 carbonyl complexes of the distibinomethane ligands of types [M(CO)5(η1dpsm)], [(OC)4M(μ-dpsm)2M(CO)4] and [(OC)4M(μ-dmsm)2M(CO)4] (M = Cr, Mo, W) have been prepared. The single crystal structures of all tungsten complexes have also been obtained. The effect of coordination on the C-Sb-C angles and the Sb-C lengths in dpsm and SbPh3 has also been examined using the Cambridge Structural Database (CSD).
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Published date: 1999
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Local EPrints ID: 463922
URI: http://eprints.soton.ac.uk/id/eprint/463922
PURE UUID: 9c03f335-89ac-48f8-92ca-774dff8242dd
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Date deposited: 04 Jul 2022 20:58
Last modified: 04 Jul 2022 20:58
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Author:
Nicholas James Holmes
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