The synthesis and structural characterisation of novel main group organometallics
The synthesis and structural characterisation of novel main group organometallics
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.
University of Southampton
2006
Nichols, Lorna Susan
(2006)
The synthesis and structural characterisation of novel main group organometallics.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
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.
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Published date: 2006
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Local EPrints ID: 466118
URI: http://eprints.soton.ac.uk/id/eprint/466118
PURE UUID: 022cce85-3439-4b38-a73c-efce06938eed
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Date deposited: 05 Jul 2022 04:24
Last modified: 05 Jul 2022 04:24
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Author:
Lorna Susan Nichols
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