Syntheses and studies on transition metal complexes involving phosphine ligands towards the syntheses of macrocyclic phosphines
Syntheses and studies on transition metal complexes involving phosphine ligands towards the syntheses of macrocyclic phosphines
The soft acyclic phosphathia ligands, Ph2P(CH2)2)nS(CH2)2PPh2 (n = 2, 3) and Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2 have been complexed to the relatively hard Cr(III) ion giving the species [CrX2(L)]PF6 (X = Cl, Br). The P2S2-donor macrocycle, Ph2[14]aneP2S2, has been reacted with Cr(III), Cu(I), Ag(I) and Au(I). A series of Au(I) complexes have been prepared with Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2 and the P2O2 ligand, Ph2P(CH2)2O(CH2)2O(CH2)2PPh2. Characterisation of these complexes includes electrospray mass spectrometry, elemental analyses, IR, UV-vis and NMR (1H, 31P) spectroscopies and in the cases of [Au(Ph2P(CH2)2O(CH2)2O(CH2)2PPh2)]PF6, [(AuBr)2(Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2)] and [(AuCl)2(Ph2P(CH2)2O(CH2)2PPh2)] structural characterisation has been achieved using single crystal X-ray crystallography. The structures show, in each case, an approximately linear P2 or PX (X = Cl, Br) coordination geometry at the Au(I) centres and reveal non-coordinating ether and thioether functionalities.
A series of secondary phosphine complexes of Rh(III), trans-[RhCl2(L)4]PF6 (L = PPh2H, PCy2H) and trans-[RhCl2(L-L)2]PF6 (L-L = PhHP(CH2)2PHPh, PhHP(CH2)3PHPh), have been prepared. Electrospray mass spectrometry, elemental analyses, IR and NMR (1H, 31P) spectroscopies have been used to characterise these species and confirm the trans coordination geometry in solutions. The X-ray crystal structures of two dinuclear phosphinite species, [(PPhOH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] and [(PPh2OH)(PPh2O)Cl(NCMe)Rh(μ-Cl)2PPh2OH)(PPh2O)(NCMe)].2thf, the former adopting a face bridged biotahedral geometry while the latter involves an edge shared bioctahedral core. Both structures show phosphinite and phosphinic acid ligands indicating the sensitivity of these Rh(III) complexes in solution.
Mono- and bidentate primary and secondary phosphines and a series of ditertiary phosphine, arsine and stibine ligands have been coordinated to Mn(I) carbonyl halides. Multinuclear NMR (1H, 13C, 31P, 55Mn) spectroscopies have been used to probe the solution behaviour, in particular the Mn-donor atom bonding in these species, X-ray crystallographic studies on several examples, including [MnCl(CO)3{o-C6H4(PH2)2}], confirms the fac-tricarbonyl arrangement. A related series of cationic Mn(I) compounds have also been investigated. A strategy for the preparation of triphosphine macrocycles based upon Mn(I) templates has been studied. The stepwise introduction of suitable phosphine precursors to Mn(I) has been achieved and template mediated ring closure reactions investigated. Characterisation of the macrocyclic products has been conducted using electrospray mass spectrometry, solution IR and multinuclear NMR spectroscopies.
University of Southampton
Pope, Simon Johnathan Albert
1999
Pope, Simon Johnathan Albert
Pope, Simon Johnathan Albert
(1999)
Syntheses and studies on transition metal complexes involving phosphine ligands towards the syntheses of macrocyclic phosphines.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The soft acyclic phosphathia ligands, Ph2P(CH2)2)nS(CH2)2PPh2 (n = 2, 3) and Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2 have been complexed to the relatively hard Cr(III) ion giving the species [CrX2(L)]PF6 (X = Cl, Br). The P2S2-donor macrocycle, Ph2[14]aneP2S2, has been reacted with Cr(III), Cu(I), Ag(I) and Au(I). A series of Au(I) complexes have been prepared with Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2 and the P2O2 ligand, Ph2P(CH2)2O(CH2)2O(CH2)2PPh2. Characterisation of these complexes includes electrospray mass spectrometry, elemental analyses, IR, UV-vis and NMR (1H, 31P) spectroscopies and in the cases of [Au(Ph2P(CH2)2O(CH2)2O(CH2)2PPh2)]PF6, [(AuBr)2(Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2)] and [(AuCl)2(Ph2P(CH2)2O(CH2)2PPh2)] structural characterisation has been achieved using single crystal X-ray crystallography. The structures show, in each case, an approximately linear P2 or PX (X = Cl, Br) coordination geometry at the Au(I) centres and reveal non-coordinating ether and thioether functionalities.
A series of secondary phosphine complexes of Rh(III), trans-[RhCl2(L)4]PF6 (L = PPh2H, PCy2H) and trans-[RhCl2(L-L)2]PF6 (L-L = PhHP(CH2)2PHPh, PhHP(CH2)3PHPh), have been prepared. Electrospray mass spectrometry, elemental analyses, IR and NMR (1H, 31P) spectroscopies have been used to characterise these species and confirm the trans coordination geometry in solutions. The X-ray crystal structures of two dinuclear phosphinite species, [(PPhOH)2(PPh2O)Rh(μ-Cl)3Rh(PPh2OH)(PPh2O)2] and [(PPh2OH)(PPh2O)Cl(NCMe)Rh(μ-Cl)2PPh2OH)(PPh2O)(NCMe)].2thf, the former adopting a face bridged biotahedral geometry while the latter involves an edge shared bioctahedral core. Both structures show phosphinite and phosphinic acid ligands indicating the sensitivity of these Rh(III) complexes in solution.
Mono- and bidentate primary and secondary phosphines and a series of ditertiary phosphine, arsine and stibine ligands have been coordinated to Mn(I) carbonyl halides. Multinuclear NMR (1H, 13C, 31P, 55Mn) spectroscopies have been used to probe the solution behaviour, in particular the Mn-donor atom bonding in these species, X-ray crystallographic studies on several examples, including [MnCl(CO)3{o-C6H4(PH2)2}], confirms the fac-tricarbonyl arrangement. A related series of cationic Mn(I) compounds have also been investigated. A strategy for the preparation of triphosphine macrocycles based upon Mn(I) templates has been studied. The stepwise introduction of suitable phosphine precursors to Mn(I) has been achieved and template mediated ring closure reactions investigated. Characterisation of the macrocyclic products has been conducted using electrospray mass spectrometry, solution IR and multinuclear NMR spectroscopies.
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Published date: 1999
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Local EPrints ID: 464006
URI: http://eprints.soton.ac.uk/id/eprint/464006
PURE UUID: ded5a1fd-547c-4314-adb8-65ed1bc4797a
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Date deposited: 04 Jul 2022 21:00
Last modified: 04 Jul 2022 21:00
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Author:
Simon Johnathan Albert Pope
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