Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.286225
Title: Structural and reactivity studies of bis(imido) complexes of molybdenum(VI)
Author: Coffey, Therese Anne
ISNI:       0000 0001 3559 7861
Awarding Body: University of London
Current Institution: University College London (University of London)
Date of Award: 1998
Availability of Full Text:
Access from EThOS:
Full text unavailable from EThOS. Please try the link below.
Access from Institution:
Abstract:
This thesis concerns the synthesis, structure and reactivity of bis(imido) complexes of molybdenum. Eleven new complexes of the type, [Mo(NR)2(S2CNEt2)2], are synthesised upon reaction of [Mo(NR)2C12(DME)] with sodium diethyldithiocarbamate, differing only by the imido substituent. Crystal structures of [Mo(NtBu)2(S2CNEt2)2] and [Mo(N(2- Me)C6H4)2(S2CNEt2)2] exhibit linear-linear imido ligation. The crystal structure of [Mo(NPh)2(S2CNEt2)2] 1, re-determined at room temperature, shows bent-linear imido ligation. VT solution nmr spectroscopy confirms the fluxionality in all complexes. Structural information is discerned from solid-state 13C nmr spectra; a direct relationship between the difference in imido angles and the difference in ppm of the ipso-carbon peaks has been established. Absolute imido angles are not calculated but comparing the angle difference with known complexes helps predict their potential reactivity. Of the structurally-unknown complexes, only those arylimido complexes without ortho-substituents suggest bending in an imido ligand. MO calculations suggest that, even for 1, there is negligible preference for linear-linear or bent-linear imido ligation. Other molecular interactions, like crystal packing forces, are cited as the dominant structural influence. Bis(imido) complexes with different co-ligands and metal centres are reported. It is suggested that [Mo(NPh)2(S2CNMe2)2] has linear-linear imido ligation, contrasting with 1. Reactivity with other simple molecules is investigated, most notable of which is the reaction with hydrogen sulfide to form disulfide complexes [Mo(NR)(S2)(S2CNEt2)2]- Reaction with acids gave bis(amido), imido-amido and also imidotris(dithiocarbamate) cations. The mechanism of the formation of [Mo(NPh)(S2)(S2CNEt2)2] upon reaction of phenyl isocyanate with [Mo(O2)(S2CNEt2)2] is studied.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.286225  DOI: Not available
Keywords: Inorganic chemistry
Share: