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Title: The synthesis and structural characterisation of novel main group organometallics
Author: Nichols, Lorna Susan
ISNI:       0000 0001 3446 037X
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 2006
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The reaction of an alkali metal precursor, a diol and a dimethylamido reagent E(NMe₂)n (E = Sn, n = 2; E = As/Sb, n = 3) has produced a wide variety of complexes, most of which are ion-contracted species. A range of heterobimetallic Sn(II)/alkali metal complexes have been synthesised. Complexes [SnBinol₂Li₂(THF)₄] 1 and [SnBinol₂Li₂(HMPA)₄] 2 are monomeric, [Sn(C10H₆O₂)₂Li₂(HMPA)₃]₂ 3 is dimeric, the complexes [Sn(C10H₆O₂)₂Li₂(DMF)₂]n 4 and [SnBinol₂Na₂(DMF)₄]n 5 are polymeric whilst [Sn8(C₆H₄O₂)12K8(THF)8]n 6 has a two dimensional network structure. Complexes 1 - 5 contain the [Sn(RO₂)₂]2- dianion. The complexes 3 and 4 contain a [O₂Li₂O₂] ladder which forms between the Sn(II) centres whilst complex 5 has a corner sharing diamond structure to the backbone of the polymer. In addition similar reactions have serendipitously produced the Sn(II) complex [{Sn₂(C₆H₄O₂)₃}{H₂NMe₂}₂. THF. ½HNMe₂] 7, the Sn(IV) complex [{SnIV(C₆H₄O₂)₃}{H₂NMe₂}₂.HMPA] 8 and the mixed Sn(IV)/alkali metal complexes [SnIV(C10H₆O₂)₃][Li(HMPA)₄]₂ 9 and the polymeric [SnIV(C₆H₄O₂)₃K₂(THF)₂]n 10. The complexes 6 and 7 contain the [Sn₂(RO₂)₃]2- dianion, whilst 8 - 10 incorporate the [SnIV (RO₂)₃]2- dianion in which the Sn centre has been oxidised to Sn(IV). Complexes 7 - 9 are ion-separated structures. The reactions of E(NMe₂)₃ (where E = As/Sb) produced the polymeric [Sb(C10H₆O₂)₃Na₃(THF)₃(DMF)₂]n 11 and the heterobimetallic complex [As₂(4-tBuC₆H₃O₂)9(4-tBuC₆H₃(O)OH)Li13(THF)10.C₆H₅CH₃] 12. Complex 12 contains the novel [Li8O₆] cage structure. This cage is also present in complex [{C₆H₅N(CH₂)₂O}₄{C₆H₅NH(CH₂)₂O}₂Li10(THF)₆]. 13. The introduction of water into the As(NMe₂)₃ reactions resulted in the formation of the As oxoanion complexes 14 - 19, where complexes 14 - 17 and 19 contain the [AsO₃] moiety. The complex [As₄(L)₂(HL)₄(H₂L)Li7O₂.C₆H₅CH₃] 14 (where H₃L = CH₃CH(OH)CH₂NHCH₂CH(OH)CH₃) contains a [Li₆O₅OH] cage. The complexes [As₂Biphenol₂Li₂O₂(TMEDA)₂] 15, [As₂Binol₂Li₂O₂(DMF)₄] 16 [As₂Binol₂Na₂O₂(DMF)₄] 17, are dimeric and display a central planar [AsOM₂OAs] M = Li/Na) moiety. [As₄Binol₄Li12O8(DMF)₄(HMPA)₄] 18 is unique in that the diol chelates to the alkali metal rather than the p-block metal. Complex [As10Biphenol10K10O10(THF)₄. THF.½C₆H₅CH₃]n 19 is a polymeric chain with branches that contain [K₄O₄]4+ tetra-anionic cubane type structures.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available