Toggling the Z-type interaction off-on in nickel-boron dihydrogen and anionic hydride complexes

Completing a series of nickel-group 13 complexes, a coordinatively unsaturated nickel-boron complex and its derivatives with a H-2, N-2, or hydride ligand were synthesized and characterized. The toggling on of a Ni(0)-B(III) inverse-dative bond enabled the stabilization of a nickel-bound anionic hydride with a remarkably low thermodynamic hydricity of Delta G degrees(H-) = 21.4 +/- 1.0 kcal mol(-1) in THF. The flexible topology of the boron metalloligand confers both favorable hydrogen binding affinity and strong hydride donicity, albeit at the cost of high H 2 basicity during deprotonation to form the hydride.

Automated summary

A nickel-boron complex and its derivatives with unique bonding structure have been synthesized, demonstrating stable nickel coordination and low thermodynamic hydricity. The flexible topology of the boron metalloligand provides favorable hydrogen binding affinity and strong hydride donicity, at the expense of high H 2 basicity during deprotonation to form the hydride.