{"doi":"10.1021/jacs.0c02742","title":"Tebbe-like and Phosphonioalkylidene and -alkylidyne Complexes of Scandium","abstract":"The bonding between scandium and carbon in a series of alkylidene- and alkylidyne-like moieties is compared. The Tebbe analogue complex (PNP)Sc(μ2-CHSiMe3)(μ2-CH3)[Al(CH3)(CH2SiMe3)] (2) (PNP– = N[2-PiPr2-4-methylphenyl]2) could be formed by adding AlMe3 to (PNP)Sc(CH2SiMe3)2 (1). The fluxional behavior of 2 is studied by a combination of 2D 13C–1H HMQC, HMBC, and other heteronuclear NMR spectroscopic experiments. The phosphonioalkylidene complex (PNP)Sc(CHPPh3)(CH3) (3) could be prepared from 2 by treatment with 2 equiv of the ylide H2CPPh3 or by methane elimination from (PNP)Sc(CH3)2 and 1 equiv of H2CPPh3. The reactivity of the alkylidene in 2 was further explored with N3Ad, which gave insertion at the Sc–C bond, yielding (PNP)Sc(CH3)[η2-N3AdCHSiMe3Al(CH3)(CH2SiMe3)] (4), while DMAP provided C–H activation across the alkylidene with loss of the Al–C bond to form (PNP)Sc(η2-NC5H3NMe2)(CH2SiMe3) (5). Utilizing the same approach that yielded 2, methane elimination in 3 could further be promoted with Al(CH3)3 to furnish the first example of a scandium phosphonioalkylidyne complex, (PNP)Sc(μ2-CPh3)(μ2-CH3)Al(CH3)2 (6). Experimental and theoretical studies were combined to compare the bonding in 2, 3, and 6, in order to understand the legitimacy of Sc–C multiple bond character.","journal":"Journal of the American Chemical Society","year":2020,"id":75490,"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":24,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9569,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2020-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":394537,"name":"Eunji Lee","orcid":"0000-0002-8925-2954","position":1,"is_corresponding":false},{"id":394538,"name":"Jun Gu","orcid":"0000-0003-2701-4421","position":2,"is_corresponding":false},{"id":394539,"name":"Michael R. Gau","orcid":"0000-0002-4790-6980","position":3,"is_corresponding":false},{"id":394540,"name":"Patrick J. Carroll","orcid":"0000-0002-8142-7211","position":4,"is_corresponding":false},{"id":344081,"name":"Mu‐Hyun Baik","orcid":"0000-0002-8832-8187","position":5,"is_corresponding":false},{"id":394541,"name":"Daniel J. Mindiola","orcid":"0000-0001-8205-7868","position":6,"is_corresponding":false},{"id":394536,"name":"Pavel Zatsepin","orcid":"0000-0001-7196-8009","position":0,"is_corresponding":true}],"reference_count":42,"raw_metadata":null,"created_at":"2026-07-18T21:46:55.856612Z","pmid":"32315531","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":[]}