{"doi":"10.1021/jacs.4c14642","title":"Synthetically Reversible, Proton-Mediated Nitrite N–O Bond Cleavage at a Dicopper Site","abstract":"High Resolution Image Download MS PowerPoint Slide A monocationic dicopper(I,I) nitrite complex [Cu 2 (μ-κ 1:κ 1 -O 2 N)DPFN][NTf 2 ] ( 2 ) (DPFN = 2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine, NTf 2 – = N(SO 2 CF 3 ) 2 – ), was synthesized by treatment of a dicopper acetonitrile complex, [Cu 2 (μ-MeCN)DPFN][NTf 2 ] 2 ( 1 ), with tetrabutylammonium nitrite ([ n Bu 4 N][NO 2 ]). DFT calculations indicate that 2 is one of three linkage isomers that are close in energy and presumably accessible in solution. Reaction of the μ-κ 1:κ 1 -O 2 N complex with p -TolSH produces nitrous acid (HONO) and the corresponding dicopper thiolate species via an acid–base exchange reaction. Notably, treatment of 2 with HNTf 2 results in N–O bond cleavage in the putative, HONO-ligated complex to form the more thermodynamically favorable nitrosyl-bridged dicopper complex [Cu 2 (μ-NO)(μ-OH)DPFN][NTf 2 ] 2 ( 4 ). This scission can be reversed via deprotonation of the hydroxy ligand with KO t Bu. X-ray diffraction studies confirmed the solid-state molecular structures of 2 and 4 . DFT calculations were used to construct a reaction coordinate diagram detailing formation of the μ-NO complex and to describe its electronic structure. The nitrosyl ligand in 4 is chemically labile, as demonstrated by its ready displacement in reactions with CO or NO 2 – .","journal":"Journal of the American Chemical Society","year":2024,"id":443854,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":8,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9499,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2024-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":1259020,"name":"Alireza Haji Seyed Javadi","orcid":null,"position":1,"is_corresponding":false},{"id":691100,"name":"Simon J. Teat","orcid":"0000-0001-9515-2602","position":2,"is_corresponding":false},{"id":391291,"name":"Thomas R. Cundari","orcid":"0000-0003-1822-6473","position":3,"is_corresponding":false},{"id":292449,"name":"T. Don Tilley","orcid":"0000-0002-6671-9099","position":4,"is_corresponding":false},{"id":1258527,"name":"Jeffrey Fernandez","orcid":"0000-0001-5618-9322","position":0,"is_corresponding":true}],"reference_count":58,"raw_metadata":null,"created_at":"2026-07-19T02:01:29.001453Z","pmid":"39655620","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}