The synthesis of bi- and multidentate antimony and bismuth ligands and their platinum metal complexes

Sheikh, Baharuddin (1981) The synthesis of bi- and multidentate antimony and bismuth ligands and their platinum metal complexes. University of Southampton, Doctoral Thesis.

Abstract

Four series of hybrid bi- and multi-dentate ligands containing Antimony donor in combination with nitrogen, oxygen or sulphur donors have been prepared, and characterised by analysis, 'H nuclear magnetic resonance spectroscopy, mass spectrometry, and by the preparation of derivatives. The four series are: o- C6) (SMethoxyphenylstibine Phi-nSb(o-C6H4OMe)n (n a 1,2,3) and (ii) Antimony-Sulphur donor ligands Ph3_n(o-C5H4SMO)n (n a 1,2,3),o-C6H4(SbMe2)(SMe), MeS(CH2)3SbR2 (R a Me, Phi and S(CH2CH2CH2SbPh2)2. (iii) Antimony-Nitrogen donor ligands Ph3_nsb(o-C6H4NMe2)q (n a 1,3), o-C6H4(NIle2)(SbMe2), Me2N(CH2)3SbR2, McN(CH2CH2SER212 and N(CH2CH2CH2 'SbR2)3 (R = Me,Ph)(iv) Open-chain tetradentates Me2Sb(CH2)20(CH2)20(CH2)2SbMe2 R2SbCH2CH2CH2N(Me)CH2CH2N(Me)CH2CH2CH2SbR2 and R2SbCH2CH2CH2SCH2CH2 SCH2CH2CH2SbR2 (R = Me ,Ph). Attempts to prepare other ligands including S(CH2CH2SbR2) , Me2NCH2CH2SbPh2, N(CH2CH2SbPh2)2, CH3C(CH2SbR2)3 and C(CH2SbR2)4 (R = Me,Ph) were unsuccessful. A limited series of hybrid bismuthines were synthesised and similarly characterised, specifically Ph3_nBi(o-C6H4OMe)n (n - 1,3), Ph3-nBi (o-C6H4s:4e)n (n = 1,3), Phi_nBi(o-C6A4NMe2)n (n = 1,3), Ph2Bi (o-C5H4C1) and o-C6H4(SbPh2)(BiPh2). A preliminary survey of the types of complexes formed by the platinum metals in their normal oxidation states with the methoxyphenylstibines, and the antimony-nitrogen donor ligands has been carried out. A series of complexes of palladium (II), platinum (II), rhodium (III) and iridium (III) have been prepared and characterised by analysis, 'H nmr, electronic and IR spectroscopy.

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