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Title: Main group imides and phosphides
Author: García, F.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2006
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This thesis concerns synthetic and structural studies of a range of main group compounds from the p-block (Groups 13 to 15 of the Periodic Table) containing phosphorus and nitrogen ligand frameworks. Chapter 1 describes the synthesis and structural studies of a diverse range of Group 13 (A1-In), Group 14 (Sn in particular), and Group 15 (As-Bi) nitrogen and phosphorus bonded complexes reported previously in the literature; the major focus being on imido (RN2-) and phosphinidine (RP2-) complexes. Chapter 2 gives experimental and general experimental details concerning the starting materials used and the twenty-five novel species produced in this thesis (which have been fully characterised using a range of analytical, spectroscopic and structural techniques). The experimental results are discussed in chapters 3-6. Chapter 3 concerns the syntheses of new Group 15-nitrogen bonded species, focusing on the use of dimmers of the type [(Me2N)E(μ-NR)]2 (E= As, Sb, Bi) as precursors on other Group 15 molecular arrangements. In Chapter 4, attempts are made to use [(RP)nAs]- anions as ligands to main group and transition metals. There studies were largely unsuccessful owing to an undesired As-As coupling reaction. However, insights into the composition of the reaction mixtures formed between E(NMe2)3 and RPH- ions have been obtained from structural studies. In Chapter 5, several novel Sn(II)-phosphinidine complexes are synthesised from the reactions of Sn(NME2)2 with RPHM (M= alkali metal). These studies help in unravelling the mechanism of the P-P bond-forming reaction; in particular suggesting that the tendency to form P-P bonds in the products stems from the increase in nucleophilicity of the RPH- anions as the size of the alkali metal is increased. Chapter 6 presents studies of Group 13 phosphinidine complexes. Several new heterometallic alkali metal-A1(III) and –In(III) complexes of this type are prepared and fully characterised, containing a variety of mixed-metal compositions.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available