{"doi":"10.1002/anie.202107475","title":"Phosphorus‐Atom Transfer from Phosphaethynolate to an Alkylidyne","abstract":"Abstract A low‐spin and mononuclear vanadium complex, ( Me nacnac)V(CO)(η 2 ‐P≡C t Bu) ( 2 ) ( Me nacnac − =[ArNC(CH 3 )] 2 CH, Ar=2,6‐ i Pr 2 C 6 H 3 ), was prepared upon treatment of the vanadium neopentylidyne complex ( Me nacnac)V≡C t Bu(OTf) ( 1 ) with Na(OCP)(diox) 2.5 (diox=1,4‐dioxane), while the isoelectronic ate‐complex [Na(15‐crown‐5)]{([ArNC(CH 2 )]CH[C(CH 3 )NAr])V(CO)(η 2 ‐P≡C t Bu)} ( 4 ), was obtained via the reaction of Na(OCP)(diox) 2.5 and ([ArNC(CH 2 )]CH[C(CH 3 )NAr])V≡C t Bu(OEt 2 ) ( 3 ) in the presence of crown‐ether. Computational studies suggest that the P‐atom transfer proceeds by [2+2]‐cycloaddition of the P≡C bond across the V≡C t Bu moiety, followed by a reductive decarbonylation to form the V−C≡O linkage. The nature of the electronic ground state in diamagnetic complexes, 2 and 4 , was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X‐ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X‐ray single‐crystal structural characterization. In combination, these data are consistent with a low‐valent vanadium ion in complexes 2 and 4 . This study represents the first example of a metathesis reaction between the P‐atom of [PCO] − and an alkylidyne ligand.","journal":"Angewandte Chemie International Edition","year":2021,"id":184081,"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":12,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.953,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2021-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":738584,"name":"Y.H. Park","orcid":"0000-0003-0434-7346","position":1,"is_corresponding":false},{"id":738585,"name":"Bimal Pudasaini","orcid":"0000-0002-6344-7040","position":2,"is_corresponding":false},{"id":738586,"name":"Takashi Kurogi","orcid":"0000-0002-8804-757X","position":3,"is_corresponding":false},{"id":394540,"name":"Patrick J. Carroll","orcid":"0000-0002-8142-7211","position":4,"is_corresponding":false},{"id":738587,"name":"David M. Kaphan","orcid":"0000-0001-5293-7784","position":5,"is_corresponding":false},{"id":738588,"name":"A. Jeremy Kropf","orcid":"0000-0002-3329-4493","position":6,"is_corresponding":false},{"id":738589,"name":"Massimiliano Delferro","orcid":"0000-0002-4443-165X","position":7,"is_corresponding":false},{"id":344081,"name":"Mu‐Hyun Baik","orcid":"0000-0002-8832-8187","position":8,"is_corresponding":false},{"id":394541,"name":"Daniel J. Mindiola","orcid":"0000-0001-8205-7868","position":9,"is_corresponding":false},{"id":507142,"name":"Mehrafshan G. Jafari","orcid":"0000-0001-6807-7520","position":0,"is_corresponding":true}],"reference_count":89,"raw_metadata":null,"created_at":"2026-07-18T23:48:26.340498Z","pmid":"34435422","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":[]}