Welcome to LookChem.com Sign In|Join Free

Article Doi

Kinetics of Nucleophilic Attack on Co-ordinated Organic Moieties. Part 19. Addition of Anilines to Tricarbonyl(1-5-η-dienyl)iron Cations

DOI: 10.1039/DT9810002489

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2489 - 2495 (1981)

Update date:2022-07-30

Topics:

Authors:

Kane-Maguire, Leon A. P.Kane-Maguire, Leon A. P.

Odiaka, Timothy I.Odiaka, Timothy I.

Turgoose, SteveTurgoose, Steve

Williams, Peter A.Williams, Peter A.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9810002489

Spectroscopic and kinetic studies of the reactions below (X=H, 2-Me, 3-Me, 4-Me, 2-Cl, 3-Cl, 4-Cl, 4-OMe, or 4-NO2) in CH3CN have provided quantitative information on the importance of basicity and steric factors in controlling amine nucleophilicity towards co-ordinated ?-hydrocarbons.Similar reactions with cations (+) (1a) and (+) (1c) have also been investigated.For the reactions of 4-methoxy- and 4-methyl-aniline with (1b), which proceed to completion, kobs.=k1.However, for the equilibrium reactions of the other less basic amines with cations (1a)-(1c) the two-term expression kobs.=k1 + k-1/(+K2Ka) is indicated.The general rate trend C6H7 > 2-MeOC6H6 > C7H9 and the low ΔH%1 and large negetive ΔS%1 values are consistent with direct addition to the dienyl rings.For attack by non-sterically crowded anilines on (1b), a Broensted plot of log k1 versus pKa of the amine conjugate acid (in H2O) has a high slope of 1.0, indicating a very strong dependence of k1 on amine basicity.A Hammett plot for this reaction gives a slope of -2.7, indicating significant bond formation and build-up of positive charge on the aniline nitrogen atom in the transition state.The steric retardation of k1 caused by blocking substituents in the 2-position of the anilines is considerably smaller than that previously found for the related additions of pyridines to cations (1a)-(1c).

View More

Products guided by the article

Product name:tricarbonyl[1-4-η-5-(N-3-methylanilino)cyclohexa-1,3-diene]iron

Cas No:81669-45-6

81669-45-6

R&D Labs maybe for 81669-45-6

Relevant to this article

Hot Product