Nickel Promoted Condensation of Acetamide and Benzonitrile for the Synthesis of an Imidoylamidine (N-NacNac) via Stable Imidoylamide Intermediate

The acetamide-benzonitrile and benzonitrile self-condensation reactions promoted by nickel­(II) hydroxy dimer 1, [Ni2(tBuDPA)2(μ-OH)2]­(ClO4)2 (tBuDPA = bis­(2-methylpyridine)tert-butylamine), for the production of imidoylamidine (IDA) ligand, N-benzimidoylbenzamidine, is investigated by UV–vis, ESI...

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Bibliographic Details
Published in:Organometallics 2019-06, Vol.38 (12), p.2512-2522
Main Authors: Guifarro Calona, Celeo R, Filatov, Alexander S, Pedro, Brian, Rybak-Akimova, Elena V
Format: Article
Language:English
Subjects:
Chemistry
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Summary:The acetamide-benzonitrile and benzonitrile self-condensation reactions promoted by nickel­(II) hydroxy dimer 1, [Ni2(tBuDPA)2(μ-OH)2]­(ClO4)2 (tBuDPA = bis­(2-methylpyridine)tert-butylamine), for the production of imidoylamidine (IDA) ligand, N-benzimidoylbenzamidine, is investigated by UV–vis, ESI-MS, FT-IR, elemental analysis, and single crystal XRD. An imidoylamide (IDD) intermediate 2, [Ni­(tBuDPA)­(IDD)]­ClO4, is trapped and fully characterized, and its reactivity with benzonitrile is confirmed. Kinetic studies gave insight into the mechanism for the formation of 2 and its conversion to 3, [Ni­(tBuDPA)­(IDA)]­ClO4. Formation of 2 is dependent on acetamide concentration, and its reactivity is affected by protic solvents, water, and methanol.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.9b00225