The reaction of dinitrito-2,2′-bipyridylcopper(II) with pyrrolidine in acetonitrile to form N-nitrosopyrrolidine

• Published in: Inorganica Chimica Acta Vol. 190; no. 1; pp. 149 - 154
• Main Authors: McKenna, Anna G., Fanning, James C.
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01.12.1991; Elsevier Science
• Subjects: Chemistry; Exact sciences and technology; Inorganic chemistry and origins of life; Kinetics and mechanism of reactions; Divalent metal Complexes; Copper II Complexes; Nitrogen heterocycle; Organic ligand; Reaction mechanism; Transition metal Complexes; Rate constant; Nitrosation
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(00)80244-3

Dinitrito-2,2′-bipyridylcopper(II), [Cu(bpy)(ONO) 2], reacts with pyrrolidine (PYR) in acetonitrile at 60 °C to form N-nitrosopyrrolidine (NPYR) and N-nitropyrrolidine (NOPYR). The reaction is first order in [Cu(bpy)(ONO) 2] with a rate constant of (4.4±1.0)x 10 −5 s −1. Reacting [Cu(bpy)Cl 2] and [(PPh 3) 2N] +NO 2 − with PYR under the same conditions produced NPYR and NOPYR at a rate that was first order in the Cu complex with approximately the same rate constant. The proposed mechanism has Cu(II) slowly reduced by nitrite to a Cu(I) complex and N 2O 4 which reacts with PYR to form NPYR and NOPYR.