Alkyldiazenido complexes, mechanisms

Alkyldiazenido complexes, mechanisms of formation, 27 223-225 Alkylfluorophosphines, 13 367-378 Alkyl ftillerides, 44 38 Alkylidiboranes cyclic, 16 215, 216 electron diffiaction studies of, 16 216 NMR of, 16 216 preparation of, 16 214, 215 Alkyllithium compounds, crystal structures, 37 83-85... 

The alkyldiazenido complexes [MoX(N2R)(dppe)2] are generally synthesized by reaction of alkyl halides with [Mo(N2)2(dppe)2]. The reaction mechanism has been elucidated in some detail,140 and is believed to involve a step in common with substitution reactions of the bis(dinitrogen) species, namely rate-controlling reversible thermal loss of N2 (equation 14). The full reaction sequence is set out in equation (15). 

Hussain, H., Leigh, G.J., Modh-Ali, H. and Pickett, C.J. Mechanism of alkylation of alkyldiazenido-complexes of molybdenum(II) and tungsten(II) influence of metal and co-ligands on the nucleophilicity of a diazenido-group J.Chem.Soc. Dalton Trans., (1986), 1473-1477... 

The nitrosation of primary alkylamines leads to deamination products. Hungarian chemists (Dozsa et al., 1984 Katho et al, 1984 Katho and Beck, 1988) investigated the kinetics by spectrophotometry and by N2-volumetric measurements in aqueous solution at pH 8.6-10.2. The results are consistent with the mechanism (4-4), in which an alkyldiazenido-iron complex 4,5 is formed followed by its decomposition to the dinitrogen-iron complex 4,6 by attack of hydroxyl ions. In the opinion of the present author, however, there are other mechanisms that would also support the kinetic data. 

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