Coordination chemistry of higher oxidation states
Coordination chemistry of higher oxidation states
Octahedral Pt(IV) complexes [Pt(L-L)X4] (X = Cl, Br, I; L-L = diamine, diphosphine, diarsine, distibine) have been prepared by oxidation of [Pt(L-L)X2] with halogen (X2) in CC14. The amine, phosphine and arsine complexes (X = Cl, Br) are very stable thermally and in solution, but the iodide and stibine complexes are of marginal stability. Chlorine oxidation of Pt(L-L)2C12 produces either [Pt(L-L)2C12]C12 or [Pt(L-L)C14] and oxidised ligand, depending on the nature of L-L. Complexes containing tridentate ligands, [Pt(L-L-L)X3]X, and tetradentate ligands [Pt(L-L-L-L)X2]X2 were also synthesised. Oxidation of [R4N][PdLX3] with the corresponding halogen (X2) in CC14 gave Pd(IV) 'anions' [R,N][PdLXS] (L = NR3, PR3, Ask, SR2, SeR2; X = Cl, Br) but attempts to obtain analogues with L = SbR3 or TeR2 failed. Neutral Pd(IV) complexes trans-[PdL2X4], prepared similarly, were much less stable. Octahedral palladium(IV) complexes [Pd(L-L)C14] (L-L = diamine, diphosphine, diarsine) were synthesised by chlorine oxidation of [Pd(L-L)C12], but a number of the corresponding [Pd(L-L)Br4] could not be prepared. Chlorine oxidation of Pd(L-L}l2 gave Pd(L-L)2C14 only in a few cases and [Pd(L-L)CI41 was the usual product. Trans- [Pd(L-L)2X2];C104)2 (L-L = diphosphine, diarsine; X = Cl, Br) were obtained by HN03/HX/HCI04 oxidation of Pd(L-L)2X2.Osmium(IV) dithioether complexes [Os(L-L)X,,] (X = Cl, Br) have been prepared from Na2OsX6 and L-L. Iridium(III) anions, [NR4][Ir(SRZ)2Cl4] and [NR4]2[lr(SR2)Cl5], are oxidised by chlorine to the corresponding Ir(IV) complexes. The [Pt(L-L)X4] (L-L = McSeCH2CH2SeMe; X = Cl, Br) were also synthesised by halogen oxidation (X2) of [Pt(L-L)X2]. The unique coordination stabilised copper(I) fluoride complex, Cu(PPh3)3F.2EtOH, prepared from CuF2.2H2O and PPh3, has been studied in detail, both in the solid state and in solution. The complexes were characterised using a variety of physical techniques (infrared, electronic and nuclear magnetic resonance spectroscopy; magnetic, electrochemical and thermogravimetric measurements) and by elemental analysis. Single crystal x-ray studies of [Pd(2,2'-bipyridyl)C14], trans- [Pd(o-C6H4(AsMe2)2)2Ci2](C104)2, Pd (cis-PhZPCH=CHPPh2)I4, trans- Me4N [Ir(SMe2)2C14] and [Cu(PPh3)3F].2EtOH are reported.
University of Southampton
1982
Gulliver, David Jeffrey
(1982)
Coordination chemistry of higher oxidation states.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Octahedral Pt(IV) complexes [Pt(L-L)X4] (X = Cl, Br, I; L-L = diamine, diphosphine, diarsine, distibine) have been prepared by oxidation of [Pt(L-L)X2] with halogen (X2) in CC14. The amine, phosphine and arsine complexes (X = Cl, Br) are very stable thermally and in solution, but the iodide and stibine complexes are of marginal stability. Chlorine oxidation of Pt(L-L)2C12 produces either [Pt(L-L)2C12]C12 or [Pt(L-L)C14] and oxidised ligand, depending on the nature of L-L. Complexes containing tridentate ligands, [Pt(L-L-L)X3]X, and tetradentate ligands [Pt(L-L-L-L)X2]X2 were also synthesised. Oxidation of [R4N][PdLX3] with the corresponding halogen (X2) in CC14 gave Pd(IV) 'anions' [R,N][PdLXS] (L = NR3, PR3, Ask, SR2, SeR2; X = Cl, Br) but attempts to obtain analogues with L = SbR3 or TeR2 failed. Neutral Pd(IV) complexes trans-[PdL2X4], prepared similarly, were much less stable. Octahedral palladium(IV) complexes [Pd(L-L)C14] (L-L = diamine, diphosphine, diarsine) were synthesised by chlorine oxidation of [Pd(L-L)C12], but a number of the corresponding [Pd(L-L)Br4] could not be prepared. Chlorine oxidation of Pd(L-L}l2 gave Pd(L-L)2C14 only in a few cases and [Pd(L-L)CI41 was the usual product. Trans- [Pd(L-L)2X2];C104)2 (L-L = diphosphine, diarsine; X = Cl, Br) were obtained by HN03/HX/HCI04 oxidation of Pd(L-L)2X2.Osmium(IV) dithioether complexes [Os(L-L)X,,] (X = Cl, Br) have been prepared from Na2OsX6 and L-L. Iridium(III) anions, [NR4][Ir(SRZ)2Cl4] and [NR4]2[lr(SR2)Cl5], are oxidised by chlorine to the corresponding Ir(IV) complexes. The [Pt(L-L)X4] (L-L = McSeCH2CH2SeMe; X = Cl, Br) were also synthesised by halogen oxidation (X2) of [Pt(L-L)X2]. The unique coordination stabilised copper(I) fluoride complex, Cu(PPh3)3F.2EtOH, prepared from CuF2.2H2O and PPh3, has been studied in detail, both in the solid state and in solution. The complexes were characterised using a variety of physical techniques (infrared, electronic and nuclear magnetic resonance spectroscopy; magnetic, electrochemical and thermogravimetric measurements) and by elemental analysis. Single crystal x-ray studies of [Pd(2,2'-bipyridyl)C14], trans- [Pd(o-C6H4(AsMe2)2)2Ci2](C104)2, Pd (cis-PhZPCH=CHPPh2)I4, trans- Me4N [Ir(SMe2)2C14] and [Cu(PPh3)3F].2EtOH are reported.
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Published date: 1982
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Local EPrints ID: 460108
URI: http://eprints.soton.ac.uk/id/eprint/460108
PURE UUID: 5e413098-93d3-4555-96d4-bd4a5e3e3d04
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Date deposited: 04 Jul 2022 17:53
Last modified: 04 Jul 2022 17:53
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Author:
David Jeffrey Gulliver
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