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Durham e-Theses
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Studies of some organonitrogen derivatives of chromium and iron

Eales, Richard James (1977) Studies of some organonitrogen derivatives of chromium and iron. Masters thesis, Durham University.



The thesis describes synthetic and structural studies of ketimlno - and amidino - complexes of chromium, and comparisons of their properties with the analagous molybdenum and tungsten derivatives. Studies of an amldino - complex of Iron are also described. The reaction of h(^5)-C(_5)H(_5)Cr(CO)(_3)Br with R(_2)CNLi (R = Ph, p-tolyl, t-butyl) produced green complexes h(^5)-C(_5)H(_5)Cr(CO)(_2)(N:Cr(_2)). Substitution of carbonyl groups in the latter could not be achieved with triphenylphosphine under a variety of conditions. The spectral properties of the complexes are discussed and compared with the corresponding molybdenum and tungsten systems. Reaction of Fe(CO)(_4)I(_2) with (p-tolyl)NLi.CMe:N(p-tolyl) produced an unidentified yellow powder. Subsequent reaction of this powder with alumina produced the orange air-sensitive complex Fe(CO)(_4){(p-tolyl)NH.CMe:N(p-tolyl)}. This complex gave no reaction, with N-bromosuccinimide. Spectral data for the complex is given and discussed. Exploratory investigations of the reaction between h(^5)-C(_5)H(_5)Cr(CO)(_3)Br and RNLi.CR':NR (R = p-tolyl, R' = Me; R = Me, R' = Ph) gave evidence for the formation of a cyclopentadienyl chromium dicarbonyl amidino complex but its instability prevented its isolation. An investigation of the reaction between Ph(_2)CNLi and h(^5)-C(_5)H(_5)cr(CO)(_3)HgBr is also described. A small quantity of h(^5)-C(_5)H(_5)Cr(CO)(_2)(N:CPh(_2)) was detected.

Item Type:Thesis (Masters)
Award:Master of Science
Thesis Date:1977
Copyright:Copyright of this thesis is held by the author
Deposited On:13 Nov 2013 16:11

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