NICKEL AND IRON NORBORNADIENYLS
Abstract
The chemistry of nickel and iron norbornadienyl compounds were studied, in particular: (1) the equilibration of syn and anti nickel norbornadienyl compounds; (2) the utility of iron norbornadienyl compounds in the synthesis of 7-substituted norbornadienes; (3) the equilibration of alkyl- and acyl-iron norbornadienyl compounds; (4) the rearrangement of iron norbornadienyl compounds to iron cycloheptatrienyl compounds; (5) the displacement of iron by nickel at carbon with nickel(I) compounds using iron norbornadienyl compounds as substrates. Chapter one deals with the involvement of nickel(I) complexes in the chemistry of the nickel norbornadienyl compounds. It has been shown that nickel(I) acts as a catalyst in the equilibration of the syn and anti nickel norbornadienyl compounds. Chapter two deals with the syn/anti equilibria of the nickel norbornadienyl compounds. It has been found that the free energy differences between the syn and anti isomers is very small; a fact that is not well understood. Chapter three deals with the synthetic utility of iron norbornadienyl compounds and their alkyl-acyl equilibria. Chapter four deals with the rearrangement of iron norbornadienyls to cycloheptatrienyls and the cycloheptatrienyls' curious lack of fluxionality. Chapter five deals with the transmetallation of iron norbornadienyls to nickel norbornadienyls using the nickel(I) reagents which catalyze the syn/anti isomerization of nickel norbornadienyls. It has been found that the replacement of iron by nickel is less facile than nickel for nickel replacement, a result in accord with literature data on the relative strengths of iron- and nickel-carbon bonds.
Degree
Ph.D.
Subject Area
Analytical chemistry
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