Syntheses and studies on transition metal complexes of antimony ligands
Syntheses and studies on transition metal complexes of antimony ligands
The complexes [AgL4]BF4 (L = SbMe3, SbEt3, SbMe2Ph, SbMePh2, SbPh3, AsPh3, PPh3, SbMe2(o-C6H4Br)), [Ag{L-L}2]BF4 (L-L = R2SbCH2SbR2, R2Sb(CH2)3SbR2 where R = Me or Ph), [CuL4]PF6 (L = SbMe2(o-C6H4Br), SbMe2Ph, SbMePh2), [Cu(R2SbCH2SbR2)2]PF6 (R = Me or Ph) and [Cu{o-C6H4(SbMe2)2}2]PF6 were prepared by the reaction of anhydrous AgBF4 or [Cu(MeCN)4]PF6 with the appropriate ligand. The structure of [Ag(SbPh3)4]BF4 has been established by X-ray crystallography and found to consist of discrete cations containing the tetrahedrally coordinated silver ion (d(Ag-Sb) = 2.7200(6) - 2.7297(6) Å). Variable temperature 63Cu and 109Ag NMR studies indicate that the complexes undergo dynamic exchange processes in solution, with [M(L)4]+ and [M(L-L)2]+ (M = Ag, Cu) as the major species present.
Rhodium(III) distibine complexes trans-(Rh(L-L)2X2]Y (L-L = Ph2Sb(CH2)3SbPh2 or o-C6H4(SbMe2)2; Y = X or BF4) and [Rh(MeC(CH2AsMe2)3)X3] (X = Cl, Br or I) have been prepared and studied by UV-Vis, 1H and 103Rh NMR spectroscopies and electrospray mass spectrometry. The 103Rh NMR spectroscopic data are reported and compared with data on related phosphine and arsine complexes. The single crystal X-ray structures of trans- [Rh(Ph2Sb(CH2)3SbPh2)2Cl2]ClO4, trans-[Rh{o-C6H4(AsMe2)2}2I2]BF4, trans-[Rh{o-C6H4(PMe2)2}2Cl2]Cl and [Rh{o-C6H4(PMe2)2}2(OH2)2]Cl3 have been obtained.
Complexes of the distibinomethane ligands, Ph2SbCH2SbPh2 (dpsm) or Me2SbCH2SbMe2 (dmsm) with iron, cobalt, manganese, nickel, chromium, molybdenum and tungsten carbonyls have been synthesised and show a variety of structures and bonding modes. The complexes have been characterised by analysis, IR and multinuclear NMR (1H, 13C{1H}, 55Mn, 59Co or 95Mo) spectroscopy and FAB mass spectrometry.
University of Southampton
1997
Hill, Angela Michelle
(1997)
Syntheses and studies on transition metal complexes of antimony ligands.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The complexes [AgL4]BF4 (L = SbMe3, SbEt3, SbMe2Ph, SbMePh2, SbPh3, AsPh3, PPh3, SbMe2(o-C6H4Br)), [Ag{L-L}2]BF4 (L-L = R2SbCH2SbR2, R2Sb(CH2)3SbR2 where R = Me or Ph), [CuL4]PF6 (L = SbMe2(o-C6H4Br), SbMe2Ph, SbMePh2), [Cu(R2SbCH2SbR2)2]PF6 (R = Me or Ph) and [Cu{o-C6H4(SbMe2)2}2]PF6 were prepared by the reaction of anhydrous AgBF4 or [Cu(MeCN)4]PF6 with the appropriate ligand. The structure of [Ag(SbPh3)4]BF4 has been established by X-ray crystallography and found to consist of discrete cations containing the tetrahedrally coordinated silver ion (d(Ag-Sb) = 2.7200(6) - 2.7297(6) Å). Variable temperature 63Cu and 109Ag NMR studies indicate that the complexes undergo dynamic exchange processes in solution, with [M(L)4]+ and [M(L-L)2]+ (M = Ag, Cu) as the major species present.
Rhodium(III) distibine complexes trans-(Rh(L-L)2X2]Y (L-L = Ph2Sb(CH2)3SbPh2 or o-C6H4(SbMe2)2; Y = X or BF4) and [Rh(MeC(CH2AsMe2)3)X3] (X = Cl, Br or I) have been prepared and studied by UV-Vis, 1H and 103Rh NMR spectroscopies and electrospray mass spectrometry. The 103Rh NMR spectroscopic data are reported and compared with data on related phosphine and arsine complexes. The single crystal X-ray structures of trans- [Rh(Ph2Sb(CH2)3SbPh2)2Cl2]ClO4, trans-[Rh{o-C6H4(AsMe2)2}2I2]BF4, trans-[Rh{o-C6H4(PMe2)2}2Cl2]Cl and [Rh{o-C6H4(PMe2)2}2(OH2)2]Cl3 have been obtained.
Complexes of the distibinomethane ligands, Ph2SbCH2SbPh2 (dpsm) or Me2SbCH2SbMe2 (dmsm) with iron, cobalt, manganese, nickel, chromium, molybdenum and tungsten carbonyls have been synthesised and show a variety of structures and bonding modes. The complexes have been characterised by analysis, IR and multinuclear NMR (1H, 13C{1H}, 55Mn, 59Co or 95Mo) spectroscopy and FAB mass spectrometry.
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Published date: 1997
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Local EPrints ID: 463046
URI: http://eprints.soton.ac.uk/id/eprint/463046
PURE UUID: fba597bd-6313-4b2b-953a-7f53ee54788b
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Date deposited: 04 Jul 2022 20:40
Last modified: 04 Jul 2022 20:40
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Author:
Angela Michelle Hill
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