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

Andrea Rossin; Maurizio Peruzzini; Fabrizio Zanobini

doi:10.1039/c0dt01836h

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

Dalton Trans. 2011 May 7;40(17):4447-52. doi: 10.1039/c0dt01836h. Epub 2011 Apr 12.

Authors

Andrea Rossin¹, Maurizio Peruzzini, Fabrizio Zanobini

Affiliation

¹ Consiglio Nazionale delle Ricerche, Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), via Madonna del Piano 10, 50019, Sesto Fiorentino (Firenze), Italy.

PMID: 21487604
DOI: 10.1039/c0dt01836h

Abstract

Reaction of the pincer hydride complex ((tBu)PCP)Ni(H) [(tBu)PCP = 2,6-C(6)H(3)(CH(2)P(t)Bu(2))(2)] with BH(3)·thf in THF at 190 K generates the corresponding borohydride complex ((tBu)PCP)Ni(BH(4)). The kinetically stable (but thermodynamically unstable) species undergoes reversible borane loss. The related fluoride complex ((tBu)PCP)Ni(F) shows the same reactivity towards BF(3)·Et(2)O, producing ((tBu)PCP)Ni(BF(4)) 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.