{"doi":"10.1021/jacs.2c00276","title":"Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V<sub>3</sub>N<sub>4</sub> Double-Diamond Core","abstract":"Transmetallation of [VCl3(THF)3] and [TlTptBu,Me] afforded [(TptBu,Me)VCl2] (1, TptBu,Me = hydro-tris(3-tert-butyl-5-methylpyrazol-1-yl)borate), which was reduced with KC8 to form a C3v symmetric VII complex, [(TptBu,Me)VCl] (2). Complex 1 has a high-spin (S = 1) ground state and displays rhombic high-frequency and -field electron paramagnetic resonance (HFEPR) spectra, while complex 2 has an S = 3/2 4A2 ground state observable by conventional EPR spectroscopy. Complex 1 reacts with NaN3 to form the VV nitride-azide complex [(TptBu,Me)V≡N(N3)] (3). A likely VIII azide intermediate en route to 3, [(TptBu,Me)VCl(N3)] (4), was isolated by reacting 1 with N3SiMe3. Complex 4 is thermally stable but reacts with NaN3 to form 3, implying a bis-azide intermediate, [(TptBu,Me)V(N3)2] (A), leading to 3. Reduction of 3 with KC8 furnishes a trinuclear and mixed-valent nitride, [{(TptBu,Me)V}2(μ4-VN4)] (5), conforming to a Robin–Day class I description. Complex 5 features a central vanadium ion supported only by bridging nitride ligands. Contrary to 1, complex 2 reacts with NaN3 to produce an azide-bridged dimer, [{(TptBu,Me)V}2(1,3-μ2-N3)2] (6), with two antiferromagnetically coupled high-spin VII ions. Complex 5 could be independently produced along with [(κ2-TptBu,Me)2V] upon photolysis of 6 in arene solvents. The putative {VIV≡N} intermediate, [(TptBu,Me)V≡N] (B), was intercepted by photolyzing 6 in a coordinating solvent, such as tetrahydrofuran (THF), yielding [(TptBu,Me)V≡N(THF)] (B-THF). In arene solvents, B-THF expels THF to afford 5 and [(κ2-TptBu,Me)2V]. A more stable adduct (B-OPPh3) was prepared by reacting B-THF with OPPh3. These adducts of B are the first neutral and mononuclear VIV nitride complexes to be isolated.","journal":"Journal of the American Chemical Society","year":2022,"id":274035,"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":10,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9454,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2022-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":942048,"name":"Dominik Fehn","orcid":"0000-0003-1377-4905","position":1,"is_corresponding":false},{"id":507140,"name":"Anders Reinholdt","orcid":"0000-0001-6637-8338","position":2,"is_corresponding":false},{"id":942049,"name":"Cristina Hernández-Prieto","orcid":"0000-0001-7477-1332","position":3,"is_corresponding":false},{"id":418709,"name":"Prajay Patel","orcid":"0000-0002-6763-6295","position":4,"is_corresponding":false},{"id":394539,"name":"Michael R. Gau","orcid":"0000-0002-4790-6980","position":5,"is_corresponding":false},{"id":394540,"name":"Patrick J. Carroll","orcid":"0000-0002-8142-7211","position":6,"is_corresponding":false},{"id":507143,"name":"J. Krzystek","orcid":"0000-0001-6088-1936","position":7,"is_corresponding":false},{"id":740888,"name":"Cong Liu","orcid":"0000-0002-2145-5034","position":8,"is_corresponding":false},{"id":502659,"name":"Andrew Ozarowski","orcid":"0000-0001-6225-9796","position":9,"is_corresponding":false},{"id":507144,"name":"Joshua Telser","orcid":"0000-0003-3307-2556","position":10,"is_corresponding":false},{"id":738589,"name":"Massimiliano Delferro","orcid":"0000-0002-4443-165X","position":11,"is_corresponding":false},{"id":507145,"name":"Karsten Meyer","orcid":"0000-0002-7844-2998","position":12,"is_corresponding":false},{"id":394541,"name":"Daniel J. Mindiola","orcid":"0000-0001-8205-7868","position":13,"is_corresponding":false},{"id":507142,"name":"Mehrafshan G. Jafari","orcid":"0000-0001-6807-7520","position":0,"is_corresponding":true}],"reference_count":197,"raw_metadata":null,"created_at":"2026-07-19T00:28:07.776043Z","pmid":"35652694","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":[]}