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The interaction of metal carbonyl compounds with organic polymers and monomers

Lyons, Michael P. (1993) The interaction of metal carbonyl compounds with organic polymers and monomers. PhD thesis, Dublin City University.

The photochemistry of W(CO)6, Mo(CO)6, and Cr(CO)6 in the presence of monomeric and polymeric triphenylphosphine ligands was investigated in toluene solution, using laser flash photolysis with 355nm excitation. The mechanism and kinetics of interaction of the primary photoproducts M(CO)5(toluene) (M = W, Mo, or Cr) with the various monomeric ligands were investigated. Interaction of the metal carbonyl photofragments with various homopolymers is also discussed. The polymerisation methods used resulted in polymers with either cyano end-groups or methyl end-groups. The nature of the end-group proved to be important in interpreting the observed reaction kinetics. The root mean square (rms) end-to-end distances of the polymer chains were also considered in rationalising the observed trends. The solution photochemistry of StyCr(CO)3, CpMn(CO)2(ri2-C8Hj4), and MeCpMn(CO)2(^-Sty)Cr(CO)3 , (Sty = Styrene; Cp = Cyclopentadienyl) was investigated in room temperature cyclohexane solution using laser flash photolysis with 355nm excitation. In StyCr(CO)3, the effect of an olefin substituent on the arene ring, on the reactivity of the photochemical intermediates produced was investigated. In the manganese complexes, olefinic ligands were directly coordinated to the metal centre, and the subsequent photochemistry was studied. The crystal and molecular structure of MeCpMn(CO)2(jU-Sty)Cr(CO)3 is also presented. This complex contains a styrene unit in an unusual bridging role between the two metal centres.
Item Type:Thesis (PhD)
Date of Award:1993
Supervisor(s):Long, Conor
Uncontrolled Keywords:Analytical chemistry; Ligands
Subjects:Physical Sciences > Photochemistry
Physical Sciences > Chemistry
DCU Faculties and Centres:DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences
Use License:This item is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 3.0 License. View License
ID Code:18972
Deposited On:26 Aug 2013 14:43 by Celine Campbell . Last Modified 26 Aug 2013 14:43

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