[Ni0L]-catalyzed cyclodimerization of 1,3-butadiene:: A density functional investigation of the influence of electronic and steric factors on the regulation of the selectivity

We present a comprehensive theoretical investigation of the influence of the ligand L on the regulation of the product selectivity for the [(NiL)-L-0]-catalyzed cyclodimerization of 1,3-butadiene. The investigation was based on density functional theory (DFT) and a combined DFT and molecular mechanics (QM/MM) approach for the real [bis(butadiene)(NiL)-L-0] catalysts with L = PMe3, I; PPh3, II; P(Pr-i)(3), III; and P(OPh)(3), IV. The role of electronic and steric effects has been elucidated for all crucial elementary steps of the entire catalytic cycle. Allylic isomerization, allylic enantioface conversion. as well as oxidative coupling are shown to be influenced to a minor extent by electronic and steric effects. In contrast, the ligand's properties have a distinct influence on the preestablished equilibrium between the eta(3),eta(1)(C-1) and biS-eta(3) forms 2 and 4, respectively, of the [(octadienediyl)(NiL)-L-II] complex and on the rate-determining reductive elimination following competing routes for generation of either VCH, cis-1,2-DVCB, or cis,cis-COD. Electronic factors are shown to predominantly determine the position of the kinetically mobile 2 4 equilibrium. 4 is the prevailing species for ligands L that are pi-acceptors (L = P(OPh)(3)) or weak sigma-donors (L = PPh3) while stronger sigma-donors (L = PMe3, P(Pr-i)(3)) displace the equilibrium to the left. Steric bulk on the ligand as well as its pi-acceptor ability act to facilitate the reductive elimination, while sigma-donor abilities serve to retard this process. Electronic and steric factors are found to not influence uniformly the reductive elimination routes with either 2 or 4 involved. The regulation of the product selectivity is elucidated on the basis of both thermodynamic and kinetic considerations.