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, N, 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 kcal mol 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 basicity during deprotonation to form the hydride.

Bioinspired Nickel Complexes Supported by an Iron Metalloligand.

Nature utilizes multimetallic sites in metalloenzymes to enable multielectron chemical transformations at ambient conditions and low overpotentials. One such example of multimetallic cooperativity can be found in the C-cluster of Ni-carbon monoxide dehydrogenase (CODH), which interconverts CO and CO. Toward a potential functional model of the C-cluster, a family of Ni-Fe bimetallic complexes was synthesized that contain direct metal-metal bonding interactions.