Higher oxidation state complexes of group Vb and VIb donor atom ligands : compounds with cobalt (III) and copper (III)
Higher oxidation state complexes of group Vb and VIb donor atom ligands : compounds with cobalt (III) and copper (III)
A series of five coordinate cobalt(III) complexes with monodentate phosphines of type [CoL2X3] have been prepared (L = PMe3, PMe2H, PEt3, PEt2Ph, PEtPh2, PPh3; X = Cl, Br) by oxidation of [CoL2X2] with NOCl or NOBr. They were characterised by spectroscopic and physical methods. The data is consistent with a trigonal bipyramidal geometry having axial phosphine ligands. In addition complexes with bidentate ligands, of type [Co(L-L)X3] (L-L = Ph2P(CH2)nPPh2, n = 4,5; X = Cl, Br) have been prepared and similarly characterised. Octahedral cobalt(III) complexes with bi- and multidentate arsines have been prepared and studied by cobalt-59 NMR. Complexes with [CoAs6]3+ moieties had cobalt-59 chemical shifts in the region -320 to + 195 ppm and exhibited solvent dependence with a shift of ca + 200 ppm on going from dmso to H2O. Complexes with [Cos4I2]+ and CoAs3I3 chromophores had resonances in the region + 4000 to + 4900 ppm. The first examples of cobalt(III) complexes with ditertiary stibines, [Co(distibine)2X2]X'(distibine = o-C6H4(SbMe2)2, Me2Sb(CH2)3SbMe2; X = X' = Cl, Br, I. distibine = o-C6H4(PMe2)(SbMe2); X = Cl, Br X' = BF4; X = X' = I) and [Colbraceo-C6H4(PMe2)(SbMe2)rbrace 3][BF4] have been prepared and the crystal structure of the pseudo-octahedral trans-[Colbraceo-C6H4(SbMe2)2 rbrace 2Cl2]2[CoCl4] determined (d(Co-Cl) = 2.263(4) A, d(Co-Sb) = 2.505(1), 2.478(1) A). Cobalt-59 NMR spectra again gave characteristic chemical shifts. The diperiodato and ditellurato complexes of copper(III), silver(III) and gold(III) have been reinvestigated and the crystal and molecular structure of Na4.64H0.36[CulbraceTeO4(OH)2 rbrace 2].16H2O determined. The anion had distorted square-planar geometry (d(Cu-O) = 1.833(4), 1.839(4) A). The sodium ions are octahedrally coordinated by water molecules forming infinite chains of face- and edge-bridging octahedra. The chains are linked by the anions, with oxygen from the tellurate coordinating to one sodium atom. The complexes have been studied by multinuclear NMR, whilst deuteriation studies together with the X-ray data establish the nature of the ligands to be (TeO4(OH)2)4- and (IO5(OH))5-. Copper(III) complexes of dibentate phosphines and arsines, of type [Cu(L-L)2[BF4]3 (L-L = o-C6H4(PMe2)(AsMe2), o-C6H4(AsMe2)2) have been reinvestigated whilst the [Cu(L-L)Cl2]BF4 (L-L = o-C6H4(PPh2)2, Ph2P(CH2)nPPh2 (n = 2,3), cis-Ph2P(CH= CH)PPh2, Cy2P(CH2)2PCy2, o-C6H4(AsPh2)2, Ph2As(CH2)2AsPh2, cis-Ph2As(CH= CH)AsPh2 have been prepared for the first time. NMR, IR and UV-visible spectroscopic data is consistent with a square-planar geometry. The crystal structure of [Culbraceo-C6H4(P(O)Ph2)2 rbrace 2Cl][CuCl4] has been determined and revealed a distorted trigonal bipyramidal structure (2xd(Cu-O)ax = 1,920(10) A, 2xd(Cu-O)eq = 2.062(10) A, d(Cu-Cl) = 2.215(9) A). The [CuCl4]2- was highly disordered.
University of Southampton
1988
Spicer, Mark Douglas
(1988)
Higher oxidation state complexes of group Vb and VIb donor atom ligands : compounds with cobalt (III) and copper (III).
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
A series of five coordinate cobalt(III) complexes with monodentate phosphines of type [CoL2X3] have been prepared (L = PMe3, PMe2H, PEt3, PEt2Ph, PEtPh2, PPh3; X = Cl, Br) by oxidation of [CoL2X2] with NOCl or NOBr. They were characterised by spectroscopic and physical methods. The data is consistent with a trigonal bipyramidal geometry having axial phosphine ligands. In addition complexes with bidentate ligands, of type [Co(L-L)X3] (L-L = Ph2P(CH2)nPPh2, n = 4,5; X = Cl, Br) have been prepared and similarly characterised. Octahedral cobalt(III) complexes with bi- and multidentate arsines have been prepared and studied by cobalt-59 NMR. Complexes with [CoAs6]3+ moieties had cobalt-59 chemical shifts in the region -320 to + 195 ppm and exhibited solvent dependence with a shift of ca + 200 ppm on going from dmso to H2O. Complexes with [Cos4I2]+ and CoAs3I3 chromophores had resonances in the region + 4000 to + 4900 ppm. The first examples of cobalt(III) complexes with ditertiary stibines, [Co(distibine)2X2]X'(distibine = o-C6H4(SbMe2)2, Me2Sb(CH2)3SbMe2; X = X' = Cl, Br, I. distibine = o-C6H4(PMe2)(SbMe2); X = Cl, Br X' = BF4; X = X' = I) and [Colbraceo-C6H4(PMe2)(SbMe2)rbrace 3][BF4] have been prepared and the crystal structure of the pseudo-octahedral trans-[Colbraceo-C6H4(SbMe2)2 rbrace 2Cl2]2[CoCl4] determined (d(Co-Cl) = 2.263(4) A, d(Co-Sb) = 2.505(1), 2.478(1) A). Cobalt-59 NMR spectra again gave characteristic chemical shifts. The diperiodato and ditellurato complexes of copper(III), silver(III) and gold(III) have been reinvestigated and the crystal and molecular structure of Na4.64H0.36[CulbraceTeO4(OH)2 rbrace 2].16H2O determined. The anion had distorted square-planar geometry (d(Cu-O) = 1.833(4), 1.839(4) A). The sodium ions are octahedrally coordinated by water molecules forming infinite chains of face- and edge-bridging octahedra. The chains are linked by the anions, with oxygen from the tellurate coordinating to one sodium atom. The complexes have been studied by multinuclear NMR, whilst deuteriation studies together with the X-ray data establish the nature of the ligands to be (TeO4(OH)2)4- and (IO5(OH))5-. Copper(III) complexes of dibentate phosphines and arsines, of type [Cu(L-L)2[BF4]3 (L-L = o-C6H4(PMe2)(AsMe2), o-C6H4(AsMe2)2) have been reinvestigated whilst the [Cu(L-L)Cl2]BF4 (L-L = o-C6H4(PPh2)2, Ph2P(CH2)nPPh2 (n = 2,3), cis-Ph2P(CH= CH)PPh2, Cy2P(CH2)2PCy2, o-C6H4(AsPh2)2, Ph2As(CH2)2AsPh2, cis-Ph2As(CH= CH)AsPh2 have been prepared for the first time. NMR, IR and UV-visible spectroscopic data is consistent with a square-planar geometry. The crystal structure of [Culbraceo-C6H4(P(O)Ph2)2 rbrace 2Cl][CuCl4] has been determined and revealed a distorted trigonal bipyramidal structure (2xd(Cu-O)ax = 1,920(10) A, 2xd(Cu-O)eq = 2.062(10) A, d(Cu-Cl) = 2.215(9) A). The [CuCl4]2- was highly disordered.
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Published date: 1988
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Local EPrints ID: 460750
URI: http://eprints.soton.ac.uk/id/eprint/460750
PURE UUID: 9c3a6784-16f1-4eef-8e66-c9038d8b7d6c
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Date deposited: 04 Jul 2022 18:29
Last modified: 04 Jul 2022 18:29
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Author:
Mark Douglas Spicer
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