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Title: Synthesis and reactions of fluoroacyl compounds of iridium
Author: Robertson, Neil
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1991
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This thesis describes the formation of iridium fluoroacyl compounds by reaction of XeF2 with Ir(I) compounds, and the reactivity of some of these fluoroacyl species. Reactions of [Ir(CO)3L2][AsF6] with XeF2 led to the fluoroacyl compounds [Ir(CO)2(COF)FL2][AsF6] for L = PEt3, PMe3, PMe2Ph, PEt2Ph and PEtPh2 but not for L = PMePh2, PPh3 and PCy3. Reactions of [IR(CO)(PMe3)4][Cl] and IR(CO)2Cl(PMe3)2 with XeF2 led to fluoroacyl containing iridium compounds but reaction of IR(CO)2Cl(PPh3)2 with XeF2 did not. Reaction of [IR(CO)2(COF)F(PEt3)2][BF4] with SiH3CN, SiH3NCS and SiH3NCO led to the complexes [IR(CO)2(C(O)X)D(PEt3)2][BF4], X = CN, NCS, NCO. SiH3N(PF2)2, SiH3NMe2, Me3SiH, Me3SiCl and SiH3Br were also reacted with [Ir(CO)2(COF)F(PEt3)2][BF4].Reaction of [Ir(CO)2(COF)F(PEt3)2[BF4] with BF3 gave [Ir(CO3F(PEt3)2[BF4]2. This compound was reacted with NMe3, PMe3, SMeEt, Pr4NCl, LiAl(OBut)3H, PEt3 and AsH3. In these reactions there was evidence for both nucleophilic attack at coordinated carbonyl ligands and for fluoride migration onto a carbonyl ligand. Products were characterised using 19F, 31P, 13C and 1H n.m.r. spectroscopy using suitable isotopic enrichments where appropriate. When isolated, products were further characterised by I.R. spectroscopy.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available