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Competing H2 versus Intramolecular C-H Activation at a Dinuclear Nickel Complex via Metal-Metal Cooperative Oxidative Addition.

Nickel(I) metalloradicals bear great potential for the reductive activation of challenging substrates but are often too unstable to be isolated. Similar chemistry may be enabled by nickel(II) hydrides that store the reducing equivalents in hydride bonds and reductively eliminate H2 upon substrate binding. Here we present a pyrazolate-based bis(-diketiminato) ligand [LPh]3- with bulky m-terphenyl substituents that can host two Ni-H units in close proximity. Complexes [LPh(NiII-H)2]- (3) are prone to intramolecular reductive H2 elimination, and an equilibrium between 3 and orthometallated dinickel(II) monohydride complexes 2 is evi-denced. 2 is shown to form via intramolecular metal-metal cooperative phenyl group C(sp2)-H oxidative addition to the dinickel(I) intermedi-ate [LPhNiI2]- (4); while NiI species have been implicated in catalytic C-H functionalization, discrete activation of C-H bonds at NiI complexes has rarely been described. The reversible H2 and C-H reductive elimination/oxidative addition equilibrium smoothly unmasks the powerful 2-electron reductant 4 from either 2 or 3, which is demonstrated by reaction with benzaldehyde. A dramatic cation effect is observed for the rate of interconversion of 2 and 3, and also for subsequent thermally driven formation of a twice orthometallated dinickel(II) complex 6. X-ray crystallographic and NMR titration studies indicate distinct interaction of the Lewis acidic cation with 2 and 3. The present system allows for unmasking of a highly reactive [LPhNiI2]- intermediate 4 either via elimination of H2 from dihydride 3 or via reductive C-H elimination from monohydride 2. The latter does not release any H2 byproduct and adds a distinct platform for metal-metal cooperative two-electron substrate reductions while circumventing the isolation of any unstable superreduced form of the bimetallic scaffold.