Nickel(ii) hydride and fluoride pincer complexes and their reactivity with Lewis acids BX3·L (X = H, L = thf; X = F, L = Et2O)

Abstract

Reaction of the pincer hydride complex (^tBuPCP)Ni(H) [^tBuPCP = 2,6-C₆H₃(CH₂P^tBu₂)₂] with BH₃·thf in THF at 190 K generates the corresponding borohydride complex (^tBuPCP)Ni(BH₄). The kinetically stable (but thermodynamically unstable) species undergoes reversible borane loss. The related fluoride complex (^tBuPCP)Ni(F) shows the same reactivity towards BF₃·Et₂O, producing (^tBuPCP)Ni(BF₄) as the main final product. The processes were followed through multinuclear NMR spectroscopy and DFT calculations, at the M06//6-31+G(d,p) level of theory.