Oxidative Addition and β‐Hydride Elimination by a Macrocyclic Dinickel Complex: Observing Bimetallic Elementary Reactions

Abstract

The dinickel(I) complex Ni2(tBuPONNOPONNO), featuring a planar macrocyclic diphosphoranide ligand tBuPONNOPONNO, offers a unique architectural platform for observing bimetallic elementary reactions. Oxidative addition reactions of alkyl halides produce dinickel(II) complexes of the type Ni2(μ‐R)(μ‐X)(tBuPONNOPONNO). However, when R = Et β‐hydride elimination is observed to form a dinickel monohydride, with the rate dependent on the nature of X. DFT studies suggest a new mechanism for bimetallic β‐hydride elimination, where the rate dependence arises from the steric pressure imposed by the X group on the opposing trans face of the dinickel macrocycle. This work enhances understanding of bimetallic elementary reactions, particularly β‐hydride elimination, which have not been well‐explored for dinuclear systems.

A one-pot reduction route to bimetallic manganese 1,8-naphthyridine complexes

“…As part of our ongoing interest in bimetallic complexes featuring 1,8-naphthyridine ligand motifs, 9,10,12,22,23 we have been investigating avenues to diversify the compatible precursors to expand the range of the accessible bimetallic products. Inspired, in part, by our previous formation of a Ni-Ni bond upon reduction with KC 8 , 12 we sought to expand the reduction approach 21 to develop a more generalisable method to access bimetallic complexes with close metal-metal interactions.…”