77674-64-7Relevant academic research and scientific papers
KINETIC OF NUCLEOPHILIC ATTACK ON COORDINATED ORGANIC MOIETIES. XIV. THE SIGNIFICANCE OF AMINE BASICITY IN DETERMINING THE NUCLEOPHILICITIES OF PYRIDINES AND ANILINES TOWARDS + CATIONS
Kane-Maguire, Leon A. P.,Odiaka, Timothy I.,Turgoose, Steve,Williams, Peter A.
, p. C5 - C9 (1980)
The second-order rate constants, k1, for addition of pyridines and anilines to the cations + (I), + (II), and +> (III) in CH3CN decrease along the series I > II > III.The Broensted relationship, log k1 = αpKa + constant, is obeyed for the addition of substituted pyridines to I and of substituted anilines to II.The slopes, α, of about 1.0 in each case indicate a strong dependence of k1 on amine basicity.These results, together with previous data on related phosphine additions, sugest a hard character for the dienyl ligands in these organometallic cations.
Kinetics of Nucleophilic Attack on Co-ordinated Organic Moieties. PART 15. Addition of p-Toluidine to Tricarbonyl(1-5-η-dienyl)iron Cations
Kane-Maguire, Leon A. P.,Odiaka, Tim I.,Williams, Peter A.
, p. 200 - 204 (2007/10/02)
The reactions of the cations 5-dienyl)(CO)3>+ (1; dienyl = C6H7, C6H6OMe-2, or C7H9) with p-toluidine in CH3CN have been shown to give the neutral adducts 4-diene.NHC6H4CH3)(CO)3> (2) according to the equation (1) + 2CH3C6H4NH2 --> (2) + +.The products have been characterised by analyses, 1H n.m.r., i.r., and field-desorption mass spectroscopy.The reactions could be reversed by the addition of acid.A stopped-flow kinetic study of the above reactions in CH3CN yields the general rate law, Rate = k.These results are rationalised in terms of two-step mechanism involving initial reversible addition (k1, k-1) of p-toluidine to the dienyl rings to form the cationic intermediates 4-diene*NH2C6H4CH3)>+ (3), followed by rapid proton loss, k2 (either solvent- or amine-assisted).For such a mechanism the kobs. values refer to k1, which is consistent with the observed order of reactivity of the cations at 0 deg C (C6H7 > C6H6OMe-2 > C7H9, 17 : 2.6 :1), and the low ΔHI and negative ΔSI values.
