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Title: Oxygen atom transfer reactions
Author: Sieker, Anke
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1994
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Oxygen atom transfer reactions in a series of early transition metal complexes in both solution and solid state were investigated, with a particular interest in O-atom transfer processes from bonded NOx (x= 1,2,3) ligands to adjacent carbonyl groups. The main objective was the synthesis and characterisation of new mixed CO/NO2- species. In Chapter 1 a general review of oxygen atom transfer reactions involving CO and NOx is given. Chapter 2 presents the results gained from reactions of M2(CO)10, ClM(CO)5 and several other carbonyl halides {M=Mn, Re} with [PPN][NO2]/[PPh4][NO2]. Chemical activation by (CH3)3NO prior to interaction with [PPN][NO2]/PPh4][NO2] has also been investigated. Complexes isolated and characterised by IR spectroscopy and X-ray diffraction include [(OC)3Mn(μ2-NO(O))22-O(NO))Mn(μ2-NO(O))22-O(NO))Mn(CO)3](PPN)2, {[CIRe(CO)3(NO2)2]C1[(CH3)3NCH2C1]3} and [Re(CO)3(ONO)3](PPN)2. Compounds such as Mn2(CO)8(PPh3)2, [Mn(CO)4C1(PPh3)] and [trans-Mn(CO)3C1(PPh3)2] substituted in part by tertiary phosphines have been tested towards their reactivity with [PPN][NO2]/[PPh4][NO2]. Reaction pathways are discussed on the basis of detailed IR spectroscopy studies. In Chapter 2.3. reactions of M(CO)6, [M(CO)5C1](Et4) {M= Cr, Mo and W} and [(OC)3Mo(μ2-C1)3Mo(CO)3](NEt4)2 with [PPN][NO2]/[PPh4](NO2] are presented. Mixed CO/NO2 species were prepared for all three metals and structurally characterised in the solid state in form of [M(CO)5(NO2)](PPh4) {M=Cr and W}. Mixed CO/NO complexes of Manganese (2.1.3.) and Chromium (2.3.2.) have been synthesised and their reactions with O2 investigated. Oxidation of the nitrosyl ligands was observed in both cases and possible reaction mechanisms are presented.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available