{"doi":"10.1021/jacs.1c10144","title":"Versatile Fe–Sn Bonding Interactions in a Metallostannylene System: Multiple Bonding and C–H Bond Activation","abstract":"The metallostannylene Cp*(iPr2MeP)(H)2Fe-SnDMP (1; Cp* = η5-C5Me5; DMP = 2,6-dimesitylphenyl), formed by hydrogen migration in a putative Cp*(iPr2MeP)HFe[Sn(H)DMP] intermediate, serves as a robust platform for exploration of transition-metal main-group element bonding and reactivity. Upon one-electron oxidation, 1 expels H2 to generate the coordinatively unsaturated [Cp*(iPr2MeP)Fe═SnDMP][B(C6F5)4] (3), which possesses a highly polarized Fe–Sn multiple bond that involves interaction of the tin lone pair with iron. Evidence from EPR and 57Fe Mössbauer spectroscopy, along with DFT studies, shows that 3 is primarily an iron-based radical with charge localization at tin. Upon reduction of 3, C–H bond activation of the phosphine ligand was observed to produce Cp*HFe(κ2-(P,Sn)═Sn(DMP)CH2CHMePMeiPr) (5). Complex 5 was also accessed via thermolysis of 1, and kinetics studies of this thermolytic pathway indicate that the reductive elimination of H2 from 1 to produce a stannylyne intermediate, Cp*(iPr2MeP)Fe[SnDMP] (A), is likely rate-determining. Evidence indicates that the production of 5 proceeds through a concerted C–H bond activation. DFT investigations suggest that the transition state for this transformation involves C–H cleavage across the Fe–Sn bond and that a related transition state where C–H bond activation occurs exclusively at the tin center is disfavored, illustrating an effect of iron–tin cooperativity in this system.","journal":"Journal of the American Chemical Society","year":2021,"id":168954,"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":30,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.958,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"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":699135,"name":"Mark A. Nesbit","orcid":"0000-0002-5642-9303","position":1,"is_corresponding":false},{"id":400388,"name":"Patrick W. Smith","orcid":"0000-0001-5575-4895","position":2,"is_corresponding":false},{"id":334945,"name":"R. David Britt","orcid":"0000-0003-0889-8436","position":3,"is_corresponding":false},{"id":292449,"name":"T. Don Tilley","orcid":"0000-0002-6671-9099","position":4,"is_corresponding":false},{"id":292447,"name":"Rex C. Handford","orcid":"0000-0002-3693-1697","position":0,"is_corresponding":true}],"reference_count":69,"raw_metadata":null,"created_at":"2026-07-18T23:46:11.334362Z","pmid":"34958213","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":[]}