{"doi":"10.1021/jacs.3c07998","title":"A [CoSiH<sub>2</sub>] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co═Si═M] (M = Co, Fe) Silicide Complexes","abstract":"High Resolution Image Download MS PowerPoint Slide Base-stabilized [BP 3 i Pr ](H) 2 CoSiH 2 (DMAP) ( 1, [BP 3 i Pr ] = PhB(CH 2 P i Pr 2 ) 3 –; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest “parent” silylene complex (LM═SiH 2 ). Complex 1 was accessed in high yields via double Si–H bond activation in SiH 4 by [BP 3 i Pr ]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1 H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si–H bonds of the SiH 2 moiety to produce bimetallic [Co═Si═M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCo I ) 2 (μ-N 2 ) (L = a tripodal ligand) resulted in the spontaneous formation of [BP 3 i Pr ](H) 2 Co═Si═Co(H) 2 L (L = [BP 2 t Bu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl) − ( 3 ); Tp″, HB(3,5-diisopropylpyrazolyl) 3 – ( 4 )) with the concomitant release of DMAP. The symmetrical silicide [BP 3 i Pr ](H) 2 Co═Si═Co(H) 2 [BP 3 i Pr ] ( 5 ) was prepared by treatment of a mixture of 1 and [BP 3 i Pr ]Co(DMAP) with 2 equiv of Ph 3 B, which in this case is required to sequester DMAP as the elimination product Ph 3 B-DMAP. A heterobimetallic silicide, [BP 3 i Pr ](H) 2 Co═Si═Fe(H) 2 [SiP 3 i Pr ] ( 7; [SiP 3 i Pr ] = PhSi(CH 2 P i Pr 2 ) 3 ), was obtained via in situ KC 8 reduction of [SiP 3 i Pr ]FeCl and subsequent addition of 1 and Ph 3 B. These transformations involving a metal–SiH 2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.","journal":"Journal of the American Chemical Society","year":2023,"id":369036,"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":2,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9502,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2023-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":292449,"name":"T. Don Tilley","orcid":"0000-0002-6671-9099","position":1,"is_corresponding":false},{"id":292447,"name":"Rex C. Handford","orcid":"0000-0002-3693-1697","position":0,"is_corresponding":true}],"reference_count":36,"raw_metadata":null,"created_at":"2026-07-19T01:15:28.704894Z","pmid":"37906296","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":[]}