Synthesis and studies on transition metal complexes incorporating thioether, selenoether and phosphine ligands
Synthesis and studies on transition metal complexes incorporating thioether, selenoether and phosphine ligands
The thioether and selenoether ligands MeE(CH2)nEMe (E = S, Se; n = 2, 3), PhE(CH2)2EPh and o-C6H4(EMe)2 (L-L) have been reacted with [Mn(CO)5X] (X = Cl, Br, I) to yield [MnX(CO)3(L-L)]. Characterisation of the complexes has been achieved using multinuclear NMR (1H, 13C{1H}, 55Mn and 77Se{1H}) and IR spectroscopies, FAB mass spectrometry, elemental analysis and, in some cases, single crystal X-ray diffraction. 55Mn NMR spectroscopic studies have enabled an δ (55Mn) range to be established; for E = S, δ (55Mn) = +67 to -567; for E = Se, δ(55Mn) = -175 to -702. These trends are discussed in terms of E → Mn bonding. In some cases pyramidal inversion was slow and distinct resonances were observed due to the presence of individual invertomers, meso-1, meso-2, and DL. The crystal structures of [MnBr(CO)3{PhS(CH2)2SPh}], [MnCl(CO)3{MeSe(CH2)3SeMe}] and [MnBr(CO)3{o-C6H4(SeMe)2}] all show a fac-tricarbonyl arrangement with a chelating ligand. The dimeric species [Mn2(CO)6(μ-Br)2(μ-MeSCH2SMe)] has also been isolated and structurally characterised.
The syntheses and characterisation of a series of Mn(I) cationic derivatives [Mn(CO)3(L)]+ have been investigated, where L = [9]aneS3, [10]anS3, MeS(CH2)2S(CH2)2SMe, MeSe(CH2)3Se(CH2)3SeMe, Ph2P(CH2)2PPh(CH2)2PPh2 and MeC(CH2PPh2)3. 55Mn NMR spectroscopic studies have allowed a comparison to be made with previous data. Single crystal X-ray studies were undertaken for [Mn(CO)3([10]aneS3)]+, [Mn(CO)3{MeS(CH2)2S(CH2)2SMe}]+ and [Mn(CO)3{MeC(CH2PPh2)3}]+.
University of Southampton
Connolly, Julie Christine
1999
Connolly, Julie Christine
Connolly, Julie Christine
(1999)
Synthesis and studies on transition metal complexes incorporating thioether, selenoether and phosphine ligands.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The thioether and selenoether ligands MeE(CH2)nEMe (E = S, Se; n = 2, 3), PhE(CH2)2EPh and o-C6H4(EMe)2 (L-L) have been reacted with [Mn(CO)5X] (X = Cl, Br, I) to yield [MnX(CO)3(L-L)]. Characterisation of the complexes has been achieved using multinuclear NMR (1H, 13C{1H}, 55Mn and 77Se{1H}) and IR spectroscopies, FAB mass spectrometry, elemental analysis and, in some cases, single crystal X-ray diffraction. 55Mn NMR spectroscopic studies have enabled an δ (55Mn) range to be established; for E = S, δ (55Mn) = +67 to -567; for E = Se, δ(55Mn) = -175 to -702. These trends are discussed in terms of E → Mn bonding. In some cases pyramidal inversion was slow and distinct resonances were observed due to the presence of individual invertomers, meso-1, meso-2, and DL. The crystal structures of [MnBr(CO)3{PhS(CH2)2SPh}], [MnCl(CO)3{MeSe(CH2)3SeMe}] and [MnBr(CO)3{o-C6H4(SeMe)2}] all show a fac-tricarbonyl arrangement with a chelating ligand. The dimeric species [Mn2(CO)6(μ-Br)2(μ-MeSCH2SMe)] has also been isolated and structurally characterised.
The syntheses and characterisation of a series of Mn(I) cationic derivatives [Mn(CO)3(L)]+ have been investigated, where L = [9]aneS3, [10]anS3, MeS(CH2)2S(CH2)2SMe, MeSe(CH2)3Se(CH2)3SeMe, Ph2P(CH2)2PPh(CH2)2PPh2 and MeC(CH2PPh2)3. 55Mn NMR spectroscopic studies have allowed a comparison to be made with previous data. Single crystal X-ray studies were undertaken for [Mn(CO)3([10]aneS3)]+, [Mn(CO)3{MeS(CH2)2S(CH2)2SMe}]+ and [Mn(CO)3{MeC(CH2PPh2)3}]+.
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Published date: 1999
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Local EPrints ID: 463550
URI: http://eprints.soton.ac.uk/id/eprint/463550
PURE UUID: 77e8d43b-6593-4143-8c2b-1667cc1b808d
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Date deposited: 04 Jul 2022 20:53
Last modified: 04 Jul 2022 20:53
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Author:
Julie Christine Connolly
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