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Updated: Jan 13, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Nitrile RC≡N Triple Bond Cleavage by a Dicopper Nitrite Complex with N2 Elimination and Formation of RCO2-
Jose Martinez Fernandez1, Ai Vy Nguyen1, Mojgan Gharaee2
1Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
Abstract:
This contribution showcases the complete scission of nitrile RC≡N bonds by [Cu2(μ-κ1:κ1-O2N)DPFN][NTf2] (1-NTf2; DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine, NTf2- = N(SO2CF3)2-), with dinitrogen elimination. These reactions produce dicopper(I,I) carboxylate complexes, [Cu2(μ-κ1:κ1-O2CR)DPFN][NTf2] (4R-NTf2). A fleeting N-nitrosamide intermediate, [Cu2(μ-N(NO)C(O)R)DPFN][NTf2] (3R-NTf2), was detected by NMR spectroscopy and observed to decompose to the final products. While none of these novel N-nitrosamide-ligated dicopper complexes could be isolated due to their thermal instability, complex 3Ph-NTf2 was crystallographically characterized, and its bonding metrics were analyzed. Furthermore, kinetic studies on the in situ formation of 3Ph-NTf2 revealed first-order dependence on both 1-NTf2 and PhCN. Quantum mechanical modeling was employed to develop a mechanistic scenario and elucidate other key intermediates in this unprecedented reaction. The nucleophilicity of the di-Cu(I) nitrite complex was further probed through its reaction with an aryl isocyanate to yield a diazotate complex, [Cu2(μ-κ1:κ1-ONNXenyl)DPFN][NTf2] (2-NTf2; Xenyl = C6H4C6H5), and CO2.
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