Huggett, Paul Gideon (1979) Acrylonitrile adducts and related systems. Doctoral thesis, Durham University.
The coordination chemistry of acrylonitrile (ACN) has-been studied with the long term view of modifying the reactivity of ACN to a Lewis acid. The first chapter of this work is a review of CAN coordination and organometallic chemistry up to July 1979 together with a comprehensive tabular summary of the literature. The coordination of ACN with relatively hard Lewis acids such as SnCl(_4), TiCl(_4), ZnCl(_2), etc., has been shown to occur via the C≡N lone pair and the repulsive interactions between ACN (as well as acetonitrile, diethyl ether, ethyl acetate and tetrahydrofuran) and GeCl(_4) and SiCl(_4) have been demonstrated by vapour pressure/composition studies. The stereochemistry of the solid adducts SnCl(_4)L(_2) where L = MeCN, Ch(_2)CHCN, Bu(^2), NC(CH(_2))(_n)CN (n = 1-4), 1,4 C(_6)H(_4)(CN)(_2), THF, Me(_2)SO and tetrahydrothiophene was investigated binuclear quadrupole resonance and infra-red spectroscopy. The hydrostannation of nitriles by HCl and SnClg has-been shown to yield β cyanoethyl tin trichloride with ACN but dimeric salts with an amidinium structure with alkyl and aryl nitriles. Finally the stoichiometric dimerization of ACN to solely adiponitrile by cobalt chloride and an electropositive metal (M = M.g, Mn, Zn) in a variety of solvents has been investigated and several plausible mechanisms proposed.
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||18 Sep 2013 15:51|