{"doi":"10.1021/jp909530u","title":"Electronic Substituent Effects in Bicyclo[1.1.1]pentane and [\n                    <i>n</i>\n                    ]Staffane Derivatives: A Quantum Chemical Study Based on Structural Variation","abstract":null,"journal":"The Journal of Physical Chemistry A","year":2010,"id":683363,"datarank":0.47032413238937254,"base_score":3.1354942159291497,"endowment":3.1354942159291497,"self_citation_contribution":0.47032413238937254,"citation_network_contribution":0.0,"self_endowment_contribution":0.47032413238937254,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":22,"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":1785166,"name":"Aldo Domenicano","orcid":null,"position":1,"is_corresponding":false},{"id":1785168,"name":"Giovanni Piacente","orcid":null,"position":2,"is_corresponding":false},{"id":1785170,"name":"Fabio Ramondo","orcid":null,"position":3,"is_corresponding":false},{"id":1785164,"name":"Anna Rita Campanelli","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"Electronic Substituent Effects in Bicyclo[1.1.1]pentane and [\n                    <i>n</i>\n                    ]Staffane Derivatives: A Quantum Chemical Study Based on Structural Variation","abstract":"The transmission of electronic substituent effects through one or more bicyclo[1.1.1]pentane units has been investigated by ascertaining how a variable substituent at a bridgehead position perturbs the geometry of a phenyl group at the opposite end of the molecule. We have analyzed the molecular structures of many bicyclo[1.1.1]pentane and [n]staffane derivatives of general formula Ph-[C(CH(2))(3)C](n)-X (n = 1-5), as obtained from molecular orbital calculations at the HF/6-31G* and B3LYP/6-311++G** levels of theory. When n = 1, the structural variation of the benzene ring is controlled primarily by the long-range polar effect of X, with significant contributions from electronegativity and pi-transfer effects. The capability of the bicyclo[1.1.1]pentane framework to transmit these short-range effects originates from the rather high electron density inside the cage and the hyperconjugative interactions occurring between substituent and framework. A set of at least two bicyclo[1.1.1]pentane units appears to be necessary to remove most of the electronegativity and pi-transfer effects. In higher [n]staffanes (n >or= 3), the very small variation of the benzene ring geometry is controlled entirely by the long-range polar effect of X. With charged groups and for n >or= 2, the potential energy of the ring deformation decreases linearly with n(-3). In Ph-C(CH(2))(3)C-X molecules, the relatively large deformation of the bicyclo[1.1.1]pentane cage is determined primarily by the electronegativity of X, similar to the electronegativity distortion of the benzene ring in Ph-X molecules. Transfer of pi electrons from substituent to cage or vice versa also plays a role in determining the cage deformation.","is_dataset_classified":null,"base_score":3.1354942159291497,"endowment":3.1354942159291497,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"20356082","pmcid":null,"openalex_id":"https://openalex.org/W2053336594","authors":[],"funders":[],"total_grants":0,"fwci":1.2687,"citation_percentile":0.77877069,"influential_citations":0,"citation_trend":[{"year":2012,"count":1},{"year":2013,"count":3},{"year":2014,"count":2},{"year":2015,"count":1},{"year":2016,"count":3},{"year":2018,"count":1},{"year":2019,"count":1},{"year":2020,"count":2},{"year":2021,"count":3},{"year":2026,"count":1}],"oa_status":"closed","license":null,"oa_locations":[{"url":"https://pubs.acs.org/doi/pdf/10.1021/jp909530u","host_type":"publisher"},{"url":"https://doi.org/10.1021/jp909530u","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/20356082","host_type":"repository"},{"url":"http://hdl.handle.net/11573/100243","host_type":"repository"}],"fields_of_study":["Free Radicals and Antioxidants","Organic Chemistry Cycloaddition Reactions","Advanced Chemical Physics Studies","Chemistry","Medicine"],"mesh_terms":[],"keywords":["Substituent","Pentane","Quantum chemical","Bicyclic molecule","Quantum","Computational chemistry","Chemistry","Variation (astronomy)","Medicinal chemistry","Organic chemistry","Physics","Molecule","Quantum mechanics"],"sdg_mappings":[],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-08-18T10:40:44.645792Z","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":[]}