{"doi":"10.1002/chem.200304767","title":"CC<sub><i>α</i></sub> Insertion: Insertion of an Alkyne into the CC Single Bond between the Carbene‐Carbon Atom and the <i>α</i>‐Carbon Atom of a Fischer Carbene Complex by an Unprecedented Metalla(di‐π‐methane) Skeletal Rearrangement","abstract":"<jats:title>Abstract</jats:title><jats:p>The first examples of insertion of a CC bond of an alkyne into a C<jats:sub>carbene</jats:sub>C<jats:sub><jats:italic>α</jats:italic></jats:sub> single bond of a carbene complex (CC<jats:sub><jats:italic>α</jats:italic></jats:sub> insertion) are reported. (<jats:italic>prim‐</jats:italic>Alkyl)carbene complexes [(OC)<jats:sub>5</jats:sub>MC(OEt)CH<jats:sub>2</jats:sub>R] (<jats:bold>1 a</jats:bold>–<jats:bold>f</jats:bold>; M=Cr, W; R=<jats:italic>n</jats:italic>Pr, C<jats:sub>7</jats:sub>H<jats:sub>7</jats:sub>, Ph) undergo CC<jats:sub><jats:italic>α</jats:italic></jats:sub> insertion of electron‐deficient alkynes [PhCCC(XEt)NMe<jats:sub>2</jats:sub>]BF<jats:sub>4</jats:sub> (<jats:bold>5 a</jats:bold>,<jats:bold>b</jats:bold>; X=O, S) to give zwitterionic carbiminium carbonylmetalates <jats:bold>3 a</jats:bold>–<jats:bold>g</jats:bold>, which are thermally transformed into (CO)<jats:sub>4</jats:sub>M chelate carbene complexes <jats:bold>4 a</jats:bold>–<jats:bold>g</jats:bold> by elimination of CO. The overall reaction is highly regio‐ and stereoselective. It involves an unprecedented metalla(di‐π‐methane) rearrangement as the key step.</jats:p>","journal":"Chemistry – A European Journal","year":2003,"id":34202,"datarank":0.5079029351295523,"base_score":2.4849066497880004,"endowment":2.4849066497880004,"self_citation_contribution":0.37273599746820013,"citation_network_contribution":0.1351669376613522,"self_endowment_contribution":0.37273599746820013,"citer_contribution":0.1351669376613522,"corpus_percentile":null,"corpus_rank":null,"citation_count":11,"citer_count":8,"citers_with_citation_signal":7,"citers_with_endowment":7,"datacite_reuse_total":2,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":177483,"name":"Rudolf Aumann","orcid":null,"position":1,"is_corresponding":false},{"id":177484,"name":"Roland Fröhlich","orcid":null,"position":2,"is_corresponding":false},{"id":177482,"name":"Seda Ünaldi","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"base_score":2.4849066497880004,"endowment":2.4849066497880004,"datacite_reuse_total":2,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"12866074","pmcid":null,"openalex_id":"https://openalex.org/W2130226541","authors":[],"funders":[],"total_grants":0,"fwci":0.7274,"citation_percentile":0.6875,"influential_citations":0,"citation_trend":[{"year":2012,"count":1},{"year":2015,"count":1},{"year":2026,"count":1}],"oa_status":"closed","license":"http://onlinelibrary.wiley.com/termsAndConditions#vor","oa_locations":[{"url":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.200304767","host_type":"publisher"},{"url":"https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.200304767","host_type":"publisher"},{"url":"https://doi.org/10.1002/chem.200304767","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/12866074","host_type":"repository"}],"fields_of_study":["Cyclopropane Reaction Mechanisms","Organometallic Complex Synthesis and Catalysis","Catalytic Cross-Coupling Reactions","Chemistry"],"mesh_terms":[],"keywords":["Carbene","Chemistry","Alkyne","Triple bond","Insertion reaction","Stereochemistry","Alkyl","Medicinal chemistry","Single bond","Stereoselectivity","Crystallography","Double bond","Polymer chemistry","Organic chemistry","Catalysis"],"sdg_mappings":[{"sdg_number":0,"sdg_label":"Clean water and sanitation"}],"linked_datasets":[{"doi":"10.5517/cc6r7qw","title":"CCDC 201088: Experimental Crystal Structure Determination","publisher":"Cambridge Crystallographic Data Centre","resource_type":"Dataset"},{"doi":"10.5517/cc6r7pv","title":"CCDC 201087: Experimental Crystal Structure Determination","publisher":"Cambridge Crystallographic Data Centre","resource_type":"Dataset"}],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-06-09T17:57:00.523320Z","pmid":null,"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":[]}