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Title: Synthetic applications of p block anions
Author: Davies, M. K.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 1997
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Chapter 1 surveys the chemistry and reactivity of Group 14 and relevant Group 15 complexes and introduces the analogies which exist between the well-established ligand behaviour of non-metallic systems and the configuration of donor functionality present in a range of main group metallo-organic compounds. Chapter 2 initially looks at the reactivity of the anion [Sn {μ-N=C(tBu)Ph}3]-, towards a variety of metals with the aim of using this complex as a tripodal ligand. However, the reaction of [Sn{μ-N=C(tBu)Ph}3Li.THF] with [CuCl] results in ligand transfer of one of the imido groups, to form [Cu{μ-N=C(tBu)Ph}]4.THF] and the presence of PPh3 fails to block this transfer, thus [Cu{μ-N=C(tBu)Ph}]4.2PPh3-THF is produced. The reaction of [Cp2Sn] with [2-LiPy] (2-Py = Pyridyl), formed from [nBuLi] with [2-PyBr], yields the Sn(IV) product [nBuSn(2-Py)3LiBr.0.5THF]. Investigations of this compound demonstrate the efficacy of the [nBuSn(2-Py)3] moiety as a robust neutral ligand. The reaction of [nBuSn(2-Py)3LiBr.0.5THF] with CuCl2 yields the Cu(I) product [nBuSn(2-Py)3CuBr.0.5THF]. However, an attempt to extend this reactivity to AgNO3 results in anion exchange, producing [nBuSn(2-Py)3LiNO3]. The Pb(II) complex [Pb(2-Py)3Li.THF] was synthesised from the reaction of [2-LiPy] with [Cp2Pb]. In Chapter 3, two alternative reaction pathways are identified in the nucleophilic substitution reactions of Group 14 metallocenes with lithiated primary amines [RNHLi]. These are exemplified by the synthesis of the primary tris(amido)stannate [(MANH)Sn(μ-NHMA)2Li.2THF] obtained from the reaction of [Cp2Sn] with [(MA)NHLi] (MA = 2-MeOC6H4), and the cubanes [ENCy4] [E = Sn, Pb ; Cy = C6H11] are prepared from [CyNHLi] and [Cp2E]. The later furnishes a new route to Group 14 imido cubanes. A study of the effects of two potent nucleophiles in the same molecule, [PhCH2N(Li)CH2)]2, with [Cp2Sn] was undertaken, yielding the dimer [{PhCH2N(CH2)2NCH2Ph}Sn]2.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available