{"doi":"10.1002/anie.202203073","title":"Isolation of an Elusive Phosphametallacyclobutadiene and Its Role in Reversible Carbon−Carbon Bond Cleavage","abstract":"Abstract The reactivity of phosphaalkynes, the isolobal and isoelectronic congeners to alkynes, with metal alkylidyne complexes is explored in this work. Treating the tungsten alkylidyne [ t BuOCO]W≡C t Bu(THF) 2 ( 1 ) with phosphaalkyne ( 10 ) results in the formation of [O 2 C( t BuC=)W{ η 2 ‐( P , C )−P≡C−Ad}(THF)] ( 13‐ t Bu THF ) and [O 2 C(AdC=)W{ η 2 ‐( P , C )−P≡C− t Bu}(THF)] ( 13‐Ad THF ); derived from the formal reductive migratory insertion of the alkylidyne moiety into a W−C arene bond. Analogous to alkyne metathesis, a stable phosphametallacyclobutadiene complex [ t BuOCO]W[ κ 2 ‐C( t Bu)PC(Ad)] ( 14 ) forms upon loss of THF from the coordination sphere of either 13‐ t Bu THF or 13‐Ad THF . Remarkably, the C−C bonds reversibly form/cleave with the addition or removal of THF from the coordination sphere of the formal tungsten(VI) metal center, permitting unprecedented control over the transformation of a tetraanionic pincer to a trianionic pincer and back. Computational analysis offers thermodynamic and electronic reasoning for the reversible equilibrium between 13‐ t Bu/Ad THF and 14 .","journal":"Angewandte Chemie International Edition","year":2022,"id":275254,"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":9,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9526,"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":944377,"name":"Alec M. Esper","orcid":"0000-0002-6023-2431","position":1,"is_corresponding":false},{"id":392174,"name":"Ion Ghiviriga","orcid":"0000-0001-5812-5170","position":2,"is_corresponding":false},{"id":275762,"name":"Khalil A. Abboud","orcid":"0000-0003-3413-9118","position":3,"is_corresponding":false},{"id":640723,"name":"Christian Ehm","orcid":"0000-0002-2538-5141","position":4,"is_corresponding":false},{"id":136529,"name":"Adam S. Veige","orcid":"0000-0002-7020-9251","position":5,"is_corresponding":false},{"id":680224,"name":"Vineet K. Jakhar","orcid":"0009-0003-3846-2286","position":0,"is_corresponding":true}],"reference_count":61,"raw_metadata":null,"created_at":"2026-07-19T00:28:16.928746Z","pmid":"35536109","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":[]}