The 4-Electron Cleavage of a N=N Double Bond by a Trimetallic TiNi2 Complex

Peter L. Dunn, Sudipta Chatterjee, Samantha N. Macmillan, Adam J. Pearce, Kyle M. Lancaster, Ian A. Tonks

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9 Scopus citations


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 μ22-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.

Original languageEnglish (US)
Pages (from-to)11762-11772
Number of pages11
JournalInorganic chemistry
Issue number17
StatePublished - Sep 3 2019

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Copyright © 2019 American Chemical Society.


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