Studies of some organonitrogen derivatives of chromium and iron

Abstract

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). 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.