{"doi":"10.1021/ja0501565","title":"A Concerted Mechanism for the Transfer of the Thiophosphinoyl Group from Aryl Dimethylphosphinothioate Esters to Oxyanionic Nucleophiles in Aqueous Solution","abstract":null,"journal":"Journal of the American Chemical Society","year":2005,"id":665980,"datarank":0.62147020895873,"base_score":4.143134726391533,"endowment":4.143134726391533,"self_citation_contribution":0.62147020895873,"citation_network_contribution":0.0,"self_endowment_contribution":0.62147020895873,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":62,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"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":1739114,"name":"Krzysztof Swierczek","orcid":null,"position":1,"is_corresponding":false},{"id":1739115,"name":"Jamie Purcell","orcid":null,"position":2,"is_corresponding":false},{"id":807736,"name":"Alvan C. Hengge","orcid":"0000-0002-5696-2087","position":3,"is_corresponding":false},{"id":1739113,"name":"Ikenna Onyido","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"A Concerted Mechanism for the Transfer of the Thiophosphinoyl Group from Aryl Dimethylphosphinothioate Esters to Oxyanionic Nucleophiles in Aqueous Solution","abstract":"Earlier work on the hydrolysis of aryl phosphinothioate esters has led to contradictory mechanistic conclusions. To resolve this mechanistic ambiguity, we have measured linear free energy relationships (beta(nuc) and beta(lg)) and kinetic isotope effects for the reactions of oxyanions with aryl dimethylphosphinothioates. For the attack of nucleophiles on 4-nitrophenyl dimethylphosphinothioate, beta(nuc) = 0.47 +/- 0.05 for phenoxide nucleophiles (pK(a) < 11) and beta(nuc) = 0.08 +/- 0.01 for hydroxide and alkoxide nucleophiles (pK(a) >or= 11). Linearity of the plot in the range that straddles the pK(a) of the leaving group (4-nitrophenoxide, pK(a) 7.14) is indicative of a concerted mechanism. The much lower value of beta(nuc) for the more basic nucleophiles reveals the importance of a desolvation step prior to rate-limiting nucleophilic attack. The reactions of a series of substituted aryl dimethylphosphinothioate esters give the same value of beta(lg) with the nucleophiles HO(-) (beta= -0.54 +/- 0.03) and PhO(-) (beta = -0.52 +/- 0.09). A significantly better Hammett correlation is obtained with sigma(-) than with sigma or sigma degrees , as expected for a transition state involving rate-limiting cleavage of the P-OAr bond. The (18)O KIE at the position of bond fission ((18)k = 1.0124 +/- 0.0008) indicates the P-O bond is approximately 40% broken, and the (15)N KIE in the leaving group ((15)k = 1.0009 +/- 0.0003) reveals the nucleofuge carries about a third of a negative charge in the transition state. Thus, both the LFER and KIE data are consistent with a concerted reaction and disfavor a stepwise mechanism.","is_dataset_classified":null,"base_score":4.143134726391533,"endowment":4.143134726391533,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"15913360","pmcid":null,"openalex_id":"https://openalex.org/W2010635899","authors":[],"funders":[{"funder_name":"NIGMS NIH HHS","grant_id":"R01 GM047297","title":null}],"total_grants":1,"fwci":3.6347,"citation_percentile":0.93167018,"influential_citations":0,"citation_trend":[{"year":2012,"count":4},{"year":2013,"count":7},{"year":2014,"count":5},{"year":2015,"count":1},{"year":2016,"count":3},{"year":2017,"count":1},{"year":2019,"count":1},{"year":2020,"count":1},{"year":2021,"count":2},{"year":2022,"count":1},{"year":2023,"count":1},{"year":2024,"count":1}],"oa_status":"closed","license":null,"oa_locations":[{"url":"https://pubs.acs.org/doi/pdf/10.1021/ja0501565","host_type":"publisher"},{"url":"https://doi.org/10.1021/ja0501565","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/15913360","host_type":"repository"},{"url":"https://digitalcommons.usu.edu/chem_facpub/422","host_type":"repository"}],"fields_of_study":["Chemical Reaction Mechanisms","Organophosphorus compounds synthesis","DNA and Nucleic Acid Chemistry","Anions","Esters","Kinetics","Phosphinic Acids","Solutions","Structure-Activity Relationship","Sulfhydryl Compounds","Water"],"mesh_terms":["Anions","Esters","Kinetics","Phosphinic Acids","Solutions","Structure-Activity Relationship","Sulfhydryl Compounds","Water"],"keywords":["Chemistry","Nucleophile","Concerted reaction","Aryl","Leaving group","Kinetic isotope effect","Hammett equation","Substituent","Medicinal chemistry","Alkoxide","Aqueous solution","Stereochemistry","Reaction rate constant","Photochemistry","Organic chemistry","Alkyl","Kinetics","Deuterium","Catalysis"],"sdg_mappings":[{"sdg_number":0,"sdg_label":"Affordable and clean energy"}],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-08-13T12:52:20.381237Z","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":[]}