Extremely Bent Cyanide Coordination at a Preorganized Dinickel Site and Assembly of a Starlike Nonanuclear Complex from the Constrained Dinickel Building Blocks

An extremely bent cyanide coordination at a dinickel scaffold is reported. Preorganization of two nickel ions is
achieved by means of a compartmental dinucleating pyrazolate ligand L-, setting up a bimetallic coordination
pocket with constrained metal−metal separation. The mixed-spin dinickel(II) complex [LNi2(CN)(MeCN)](ClO4)2
(1) has been characterized by X-ray diffraction. The MeCN bound to the high-spin nickel(II) ion can be removed
or replaced by other ligands, e.g., by the cyanide ligand of a tetracyanonickelate(II) moiety to give the starlike
nonanuclear complex {[LNi2(CN)]4[Ni(CN)4]}(ClO4)6 (2) that contains four of the constrained pyrazolate-based
dinickel(II) fragments grouped around a central tetracyanonickelate(II) unit, as revealed by X-ray crystallography.
Spectral and electrochemical properties of 1 and 2 are reported, and the formation of reduced mixed-valent NiINiII
species is investigated by IR and UV/vis spectroelectrochemistry.