Selective Transformation of Nickel-Bound Formate to CO or C-C Coupling Products Triggered by Deprotonation and Steered by Alkali-Metal Ions.

The complexes [LtBu Ni(OCO-κ2 O,C)]M3 [N(SiMe3 )2 ]2 (M=Li, Na, K), synthesized by deprotonation of a nickel formate complex [LtBu NiOOCH] with the corresponding amides M[N(SiMe3 )2 ], feature a NiII -CO2 2- core surrounded by Lewis-acidic cations (M+ ) and the influence of the latter on the behavior and reactivity was studied. The results point to a decrease of CO2 activation within the series Li, Na, and K, which is also reflected in the reactivity with Me3 SiOTf leading to the liberation of CO and formation of a Ni-OSiMe3 complex. Furthermore, in case of K+ , the {[K3 [N(SiMe3 )2 ]2 }+ shell around the Ni-CO2 2- entity was shown to have a large impact on its stabilization and behavior. If the number of K[N(SiMe3 )2 ] equivalents used in the reaction with [LtBu NiOOCH] is decreased from 3 to 0.5, the deprotonated part of the precursor enters a complex reaction sequence with formation of [LtBu NiI (μ-OOCH)NiI LtBu ]K and [LtBu Ni(C2 O4 )NiLtBu ]. The same reaction at higher concentrations additionally led to the formation of a unique hexanuclear NiII complex containing both oxalate and mesoxalate ([O2 C-CO2 -CO2 ]4- ) ligands.