Abstract
The cyclodimerization of norbornadiene-2,5 (NBD) catalyzed by the systems formed on the basis of bis(ηy3-allyl)nickel and organophosphorus compounds and the process kinetics are studied. The formation rate of all products follows the overall second-order rate law: first order with respect to the catalyst and NBD. The addition of phosphines and phosphites substantially decreases the reaction rate compared to that in nickel systems containing no organophosphorus additives. The influence of the phosphine ligand structure and temperature on the ratio of the reaction products is studied. The blocking of one coordination site on the nickel atom changes the process kinetics. The loss of two vacancies results in the loss of the catalytic activity of the system. A mechanism explaining the stoichiometry and composition of the reaction products is proposed.
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