The redox properties of Ni complexes bound to a new ligand, [DMC-nit] +, where a N-heterocyclic nitrenium group is anchored on a 1,4,8,11-tetraazacyclotetradecane backbone, have been examined using spectroscopic and DFT methods. Ligand-based [(DMC-nit)Ni]2+/+ reduction and metal-based [(DMC-nit)Ni]2+/3+ oxidation processes have been established for the [(DMC-nit)Ni]+/2+/3+ redox series, which represents the first examples of nitrenium nitrogen (Nnit)-bound first-row transition-metal complexes. An unprecedented bent binding mode of Nnit in [(DMC-nit)Ni]2+ is observed, which possibly results from the absence of any Nnit→Ni σ-donation. For the corresponding [(DMC-nit)Ni(F)]2+ complex, σ-donation is dominant, and hence a coplanar arrangement at Nnit is predicted by DFT. The binding of the triazolium ion to Ni enables new chemistry (formate oxidation) that is not observed in a derivative that lacks this functional group. Thus the N-heterocyclic nitrenium ligand is a potentially useful and versatile reagent in transition-metal-based catalysis. © 2013 American Chemical Society.

Heims, F., Pfaff, F., Abram, S., Farquhar, E., Bruschi, M., Greco, C., et al. (2014). Redox Non-innocence of a N-Heterocyclic Nitrenium Cation Bound to a Nickel–Cyclam Core. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(2), 582-585 [10.1021/ja4099559].

Redox Non-innocence of a N-Heterocyclic Nitrenium Cation Bound to a Nickel–Cyclam Core

BRUSCHI, MAURIZIO;GRECO, CLAUDIO;
2014

Abstract

The redox properties of Ni complexes bound to a new ligand, [DMC-nit] +, where a N-heterocyclic nitrenium group is anchored on a 1,4,8,11-tetraazacyclotetradecane backbone, have been examined using spectroscopic and DFT methods. Ligand-based [(DMC-nit)Ni]2+/+ reduction and metal-based [(DMC-nit)Ni]2+/3+ oxidation processes have been established for the [(DMC-nit)Ni]+/2+/3+ redox series, which represents the first examples of nitrenium nitrogen (Nnit)-bound first-row transition-metal complexes. An unprecedented bent binding mode of Nnit in [(DMC-nit)Ni]2+ is observed, which possibly results from the absence of any Nnit→Ni σ-donation. For the corresponding [(DMC-nit)Ni(F)]2+ complex, σ-donation is dominant, and hence a coplanar arrangement at Nnit is predicted by DFT. The binding of the triazolium ion to Ni enables new chemistry (formate oxidation) that is not observed in a derivative that lacks this functional group. Thus the N-heterocyclic nitrenium ligand is a potentially useful and versatile reagent in transition-metal-based catalysis. © 2013 American Chemical Society.
Articolo in rivista - Articolo scientifico
Nitrenium Cation
English
2014
136
2
582
585
none
Heims, F., Pfaff, F., Abram, S., Farquhar, E., Bruschi, M., Greco, C., et al. (2014). Redox Non-innocence of a N-Heterocyclic Nitrenium Cation Bound to a Nickel–Cyclam Core. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(2), 582-585 [10.1021/ja4099559].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/49602
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