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Title: A study of the structural diversity of complexes derived from the reactions of cyclo-(PhAs)6 and cyclo-(PhP)6 with transition metal complexes
Author: de Silva, W. R. M.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 1998
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Abstract:
Chapter One provides a general introduction to the thesis by reviewing the reactivity of group 15 homoatomic rings of arsenic and phosphorus toward various organometallic complexes and the structures of the reaction product. Part A deals with metal complexes ligated by various fragments containing arsenic derived from five and six-membered rings of arsenic atoms. Part B covers metal complexes ligated by various fragments containing phosphorus derived from the reaction between three, four and five-membered rings containing phosphorus and metal complexes. Chapter Two is divided into two sections. Section A describes a study of the reactions of cyclo-(PhAs)6 and cyclo-(PhP)6 with [Co2(μ-R1C≍CR2)(CO)6] (R1 = R2 = H, Ph; R1 = Ph; R2 = H; R1 = Me, R2 = H). The further reactivity of the substituted product [Co2(μ-HC≍CH)){μ-cyclo-(PhAs)6}(CO)4] towards thermolysis and other metal centres is investigated. The X-ray crystal structures of [Co2(μ-HC≍CH)){μ-cyclo-(PhAs)6}(CO)4], [Co2(μ-PhC≍CPh)){μ-cyclo-(PhAs)6}(CO)4] and [Co2(μ-HC≍CH)){μ-cyclo-(PhP)6} (CO)4] are presented. In Section B the reaction of cyclo-(PhAs)6 with [Co2(CO)8] is investigated. The further reactivity of the complex [Co43-AsPh)(μ4221-As4Ph4)(CO)10] obtained from this reaction, towards thermolysis, phosphites, phosphines and other metal centres is explored. The X-ray crystal structures of [Co43-AsPh)(μ4221-As4Ph4)(CO)10], [Co43-AsPh)2321-As2Ph2)(CO)10], [Co43-AsPh)(μ4221-As2Ph2){P(OMe)3}3(CO)7] and [Co43-AsPh)2321-As2Ph2(Fe(CO)4)}(CO)10] are presented. In Chapter Three the reactions of cyclo-(PhAs)6 and cyclo-(PhP)6 with [Ru3(NCMe)2(CO)10], [Ru3(CO)12] and [Fe3(CO)12] are described. The X-ray crystal structures of [Ru3{μ-cyclo-(PhAs)6}(CO)10], [Ru43-AsPh)2(CO)13], [Ru64-PPh)33-PPh)2(CO)12], [Fe2(μ-P4Ph4)(CO)6] and [Fe44-P2Ph2)2(CO)12] are presented.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.598456  DOI: Not available
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