Nitrosonium Reactivity of (NHC)Copper(I) Sulfide Complexes

Abraham J Jordan; Rebecca K Walde; Kelly M Schultz; John Bacsa; Joseph P Sadighi

doi:10.1021/acs.inorgchem.9b01676

Nitrosonium Reactivity of (NHC)Copper(I) Sulfide Complexes

Inorg Chem. 2019 Aug 5;58(15):9592-9596. doi: 10.1021/acs.inorgchem.9b01676. Epub 2019 Jul 22.

Authors

Abraham J Jordan¹, Rebecca K Walde¹, Kelly M Schultz², John Bacsa^{1

3}, Joseph P Sadighi¹

Affiliations

¹ School of Chemistry and Biochemistry , Georgia Institute of Technology , Atlanta , Georgia 30332-0400 , United States.
² Murdock Hall, Department of Chemistry , Linfield College , McMinnville , Oregon 97128 , United States.
³ X-ray Crystallography Center, Department of Chemistry , Emory University , 1515 Dickey Drive , Atlanta , Georgia 30322 , United States.

PMID: 31328510
DOI: 10.1021/acs.inorgchem.9b01676

Abstract

This study examines the reactivity of a series of copper(I) sulfide complexes stabilized by the expanded-ring N-heterocyclic carbene (NHC) 1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene (7Dipp) toward the nitrosonium ion (NO⁺). 7Dipp is shown to support neutral sulfide- and disulfide-bridged dicopper(I) complexes, as well as mononuclear copper(I) hydrosulfide. The addition of NO⁺ to each of these results in the formation of NHC-supported copper(I) cations and elemental sulfur. Reduction of copper(I) to copper(0) is observed upon reaction of NO⁺ with dicopper(I) sulfide or disulfide, whereas ammonium ion formation is observed upon reaction of copper(I) hydrosulfide with NO⁺. Ammonium ion formation is likewise observed upon reaction of NO⁺ with (7Dipp)copper(I) hydride.