A Stable Crystalline Copper(I)-N2 O Complex Stabilized as the Salt of a Weakly Coordinating Anion

Vadim Zhuravlev; Przemysław J Malinowski

doi:10.1002/anie.201806836

A Stable Crystalline Copper(I)-N₂ O Complex Stabilized as the Salt of a Weakly Coordinating Anion

Angew Chem Int Ed Engl. 2018 Sep 3;57(36):11697-11700. doi: 10.1002/anie.201806836. Epub 2018 Aug 6.

Authors

Vadim Zhuravlev^{1

2}, Przemysław J Malinowski²

Affiliations

¹ Faculty of Physics, University of Warsaw, Pasteura 5, 02093, Warsaw, Poland.
² Centre of New Technologies, University of Warsaw, Banacha 2c, 02097, Warsaw, Poland.

PMID: 30020562
DOI: 10.1002/anie.201806836

Abstract

Nitrous oxide is considered a poor ligand, and therefore only a handful of well-defined metal-N₂ O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag₂ I₂ ][An]₂ ([An]^- =[Al(OC(CF₃ )₃ )₄ ]^- ) in perfluorinated hexane leads to Cu^I [An], the first auxiliary ligand-free Cu^I salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N₂ O)[An], where the Cu-N₂ O bond is by far the strongest among all other molecular metal-N₂ O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N₂ O)[An] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu⁺ -N₂ O system and confirm N-end coordination of the ligand.

Keywords: Lewis acid; copper; nitrous oxide; oxidizer; weakly coordinating anions.