Sixth Ligand Induced HNO/NO- Release by a Five-Coordinated Cobalt(II) Nitrosyl Complex Having a {CoNO}8 Configuration

Shankhadeep Saha; Sayani Maity; Rakesh Mazumdar; Bapan Samanta; Riya Ghosh; Ankur K Guha; Biplab Mondal

doi:10.1021/acs.inorgchem.3c01124

Sixth Ligand Induced HNO/NO^- Release by a Five-Coordinated Cobalt(II) Nitrosyl Complex Having a {CoNO}⁸ Configuration

Inorg Chem. 2023 Oct 23;62(42):17074-17082. doi: 10.1021/acs.inorgchem.3c01124. Epub 2023 Oct 9.

Authors

Shankhadeep Saha¹, Sayani Maity¹, Rakesh Mazumdar¹, Bapan Samanta¹, Riya Ghosh¹, Ankur K Guha², Biplab Mondal¹

Affiliations

¹ Department of Chemistry, Indian Institute of Technology (IIT) Guwahati, Guwahati, Assam 781039, India.
² Advanced Computational Chemistry Center, Department of Chemistry, Cotton University, Guwahati, Assam781001, India.

PMID: 37811901
DOI: 10.1021/acs.inorgchem.3c01124

Abstract

Nitroxyl (HNO) and nitroxide (NO^-) anion, the one-electron-reduced form of nitric oxide (NO), have been shown to have distinct advantages over NO from pharmacological and therapeutic points of view. However, the role of nitroxyl in chemical biology has not yet been studied as extensively as that of NO. Consequently, only a few examples of HNO donors such as Angeli's salt, Piloty's acid, or acyl- and acyloxynitroso derivatives are known. However, the intrinsic limitations of all of these hinder their widespread utility. Metal nitrosyl complexes, although few examples, could serve as an efficient HNO donor. Here, a cobalt nitrosyl complex of the {CoNO}⁸ (1) configuration has been reported. This complex in the presence of a sixth ligand [BF₄^-, DTC^- (diethyldithiocarbamate anion), or imidazole] releases/donates HNO/NO^-. This has been confirmed using well-known HNO/NO^- acceptors like [Fe(TPP)Cl] and [Fe(DTC)₃]. The HNO release has been authenticated further by the detection and estimation of N₂O using gas chromatography-mass spectroscopy as well as its reaction with PPh₃.