The synthesis and reactivity of a new trimetallic complex Ti(NP)4Ni2 (NP = 2-diphenylphosphinopyrrolide) (3) is reported. Single-crystal X-ray diffraction and X-ray absorption studies point to a unique bonding motif: a d10-d10, Ni0-Ni0 bond stabilized by a proximal d0 TiIV metal center. The coordination chemistry of 3 with a variety of L (L = isocyanide and alkyne) donors has also been explored. In the case of isocyanide coordination, the Ni-Ni bond is broken, while diphenylacetylene binding results in a symmetric butterfly μ2-κ2-alkyne bridge across the Ni-Ni moiety. Finally, complex 3 is capable of the 4-electron cleavage of the N=N double bond in benzo[c]cinnoline, the first example of N=N bond cleavage by Ni. The resulting product, 7, has been characterized structurally and spectroscopically, and the mechanistic implications are discussed in the context of metal-metal cooperativity.
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