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5697444 
Book/Book Chapter 
Structure–Reactivity Relationships in the Cyclo-Oligomerization of 1,3-Butadiene Catalyzed by Zerovalent Nickel Complexes 
Tobisch, S 
2003 
Academic Press 
Advances in Organometallic Chemistry 
49 
167-224 
WOS:000185824800005 
Publisher Summary This chapter reviews the structure–reactivity relationships in the cyclo-oligomerization of 1, 3-butadiene catalyzed by zerovalent nickel complexes. It outlines the known mechanistic details for the C8- and C12-cyclo-oligomer generating channels together with the catalytic cycles followed by a brief description of the computational approach employed and the chosen catalyst models. The results of the theoretical exploration of critical elementary steps of the complete catalytic cycles are presented. The influence of electronic and steric properties of the ancillary ligand L on the thermodynamic and kinetic aspects of individual steps of the C8-channel is analyzed. The chapter also proposes, respectively, theoretically well-founded catalytic schemes for the C8- and C12-cyclo-oligomer generation channels, followed by an elucidation of the regulation of the product selectivity for the two channels. The rationalization of the C8 -and:C12-cyclo-oligomer selectivity for the two major types of catalysts that arise from the subtle interplay between the two channels is also presented.