{"id":"https://openalex.org/W7220834908","doi":"https://doi.org/10.26434/chemrxiv.15010004/v1","title":"Transition-Metal-Controlled \u03b1-C\u2013H Acidity in Keto\u2013Enol Tautomers: A DFT Study of Metal, Tautomer, and Substituent Effects","display_name":"Transition-Metal-Controlled \u03b1-C\u2013H Acidity in Keto\u2013Enol Tautomers: A DFT Study of Metal, Tautomer, and Substituent Effects","publication_year":2026,"publication_date":"2026-10-06","ids":{"openalex":"https://openalex.org/W7220834908","doi":"https://doi.org/10.26434/chemrxiv.15010004/v1"},"language":"en","primary_location":{"id":"doi:10.26434/chemrxiv.15010004/v1","doi":"https://doi.org/10.26434/chemrxiv.15010004/v1","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.15010004/v1","pdf_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010004/v1","source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by","license_id":"https://openalex.org/licenses/cc-by","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"},"volume":null,"type":"preprint","is_traditional":true,"indexed_in":["crossref"],"open_access":{"is_oa":true,"oa_status":"green","oa_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010004/v1","any_repository_has_fulltext":true},"authorships":[{"author_position":"first","author":{"id":"https://openalex.org/A5091994338","display_name":"Amir Mahdian","orcid":"https://orcid.org/0009-0006-0480-477X","observed_orcids":["https://orcid.org/0009-0006-0480-477X"]},"institutions":[{"id":"https://openalex.org/I9927081","display_name":"Aalto University","ror":"https://ror.org/020hwjq30","country_code":"FI","type":"education","lineage":["https://openalex.org/I9927081"]}],"countries":["FI"],"is_corresponding":false,"raw_author_name":"Amir Mahdian","raw_affiliation_strings":["Aalto University","Department of Chemistry and Material Science, School of chemical Engineering"],"raw_orcid":"https://orcid.org/0009-0006-0480-477X","affiliations":[{"raw_affiliation_string":"Aalto University","institution_ids":["https://openalex.org/I9927081"]},{"raw_affiliation_string":"Department of Chemistry and Material Science, School of chemical Engineering","institution_ids":[]}]},{"author_position":"last","author":{"id":"https://openalex.org/A5074326879","display_name":"Kari E. Laasonen","orcid":"https://orcid.org/0000-0002-4419-7824","observed_orcids":["https://orcid.org/0000-0002-4419-7824"]},"institutions":[{"id":"https://openalex.org/I9927081","display_name":"Aalto University","ror":"https://ror.org/020hwjq30","country_code":"FI","type":"education","lineage":["https://openalex.org/I9927081"]}],"countries":["FI"],"is_corresponding":false,"raw_author_name":"Kari Laasonen","raw_affiliation_strings":["Aalto University","Department of Chemistry and Material Science, School of chemical Engineering"],"raw_orcid":null,"affiliations":[{"raw_affiliation_string":"Aalto University","institution_ids":["https://openalex.org/I9927081"]},{"raw_affiliation_string":"Department of Chemistry and Material Science, School of chemical Engineering","institution_ids":[]}]}],"institutions":[],"countries_distinct_count":1,"institutions_distinct_count":1,"corresponding_author_ids":[],"corresponding_institution_ids":["https://openalex.org/I9927081"],"apc_list":null,"apc_paid":null,"fwci":null,"has_fulltext":true,"cited_by_count":0,"citation_normalized_percentile":null,"cited_by_percentile_year":null,"biblio":{"volume":null,"issue":null,"first_page":null,"last_page":null},"is_retracted":false,"is_paratext":false,"is_xpac":false,"primary_topic":{"id":"https://openalex.org/T12191","display_name":"Physical Organic Chemistry and Reaction Kinetics","score":0.5835000276565552,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},"topics":[{"id":"https://openalex.org/T12191","display_name":"Physical Organic Chemistry and Reaction Kinetics","score":0.5835000276565552,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T10092","display_name":"Organometallic Complex Synthesis and Catalysis","score":0.1940000057220459,"subfield":{"id":"https://openalex.org/subfields/1605","display_name":"Organic Chemistry"},"field":{"id":"https://openalex.org/fields/16","display_name":"Chemistry"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}},{"id":"https://openalex.org/T10002","display_name":"Advanced Chemical Physics Studies","score":0.044199999421834946,"subfield":{"id":"https://openalex.org/subfields/3107","display_name":"Atomic and Molecular Physics, and Optics"},"field":{"id":"https://openalex.org/fields/31","display_name":"Physics and Astronomy"},"domain":{"id":"https://openalex.org/domains/3","display_name":"Physical Sciences"}}],"keywords":[{"id":"https://openalex.org/keywords/keto-enol-tautomerism","display_name":"keto-enol tautomerism","score":0.9290000200271606},{"id":"https://openalex.org/keywords/gold-iii-complexes","display_name":"gold(III) complexes","score":0.8479999899864197},{"id":"https://openalex.org/keywords/metal-coordination","display_name":"metal coordination","score":0.6050000190734863},{"id":"https://openalex.org/keywords/deprotonation","display_name":"deprotonation","score":0.7059999704360962},{"id":"https://openalex.org/keywords/substituent-effects","display_name":"substituent effects","score":0.7770000100135803},{"id":"https://openalex.org/keywords/electron-withdrawing-substituents","display_name":"electron-withdrawing substituents","score":0.7990000247955322},{"id":"https://openalex.org/keywords/electron-donating-substituents","display_name":"electron-donating substituents","score":0.8190000057220459},{"id":"https://openalex.org/keywords/activation-barrier","display_name":"activation barrier","score":0.5740000009536743},{"id":"https://openalex.org/keywords/porphyrin-complexes","display_name":"porphyrin complexes","score":0.7699999809265137},{"id":"https://openalex.org/keywords/cobalt-iii-complexes","display_name":"cobalt(III) complexes","score":0.718999981880188},{"id":"https://openalex.org/keywords/rhodium-iii-complexes","display_name":"rhodium(III) complexes","score":0.9929999709129333},{"id":"https://openalex.org/keywords/tautomer-stability","display_name":"tautomer stability","score":0.4359999895095825},{"id":"https://openalex.org/keywords/pka","display_name":"pKa","score":0.43299999833106995}],"concepts":[{"id":"https://openalex.org/C111233374","wikidata":"https://www.wikidata.org/wiki/Q334640","display_name":"Tautomer","level":2,"score":0.9556999802589417},{"id":"https://openalex.org/C118629725","wikidata":"https://www.wikidata.org/wiki/Q2686738","display_name":"Deprotonation","level":3,"score":0.8817999958992004},{"id":"https://openalex.org/C2778689049","wikidata":"https://www.wikidata.org/wiki/Q898422","display_name":"Substituent","level":2,"score":0.8633000254631042},{"id":"https://openalex.org/C185592680","wikidata":"https://www.wikidata.org/wiki/Q2329","display_name":"Chemistry","level":0,"score":0.8021000027656555},{"id":"https://openalex.org/C152365726","wikidata":"https://www.wikidata.org/wiki/Q1048589","display_name":"Density functional theory","level":2,"score":0.6273000240325928},{"id":"https://openalex.org/C70050531","wikidata":"https://www.wikidata.org/wiki/Q899089","display_name":"Delocalized electron","level":2,"score":0.5260999798774719},{"id":"https://openalex.org/C544153396","wikidata":"https://www.wikidata.org/wiki/Q11426","display_name":"Metal","level":2,"score":0.5253999829292297},{"id":"https://openalex.org/C147597530","wikidata":"https://www.wikidata.org/wiki/Q369472","display_name":"Computational chemistry","level":1,"score":0.5134999752044678},{"id":"https://openalex.org/C2777495281","wikidata":"https://www.wikidata.org/wiki/Q408053","display_name":"Enol","level":3,"score":0.44029998779296875},{"id":"https://openalex.org/C147535893","wikidata":"https://www.wikidata.org/wiki/Q408053","display_name":"Keto\u2013enol tautomerism","level":3,"score":0.33899998664855957},{"id":"https://openalex.org/C168900304","wikidata":"https://www.wikidata.org/wiki/Q171407","display_name":"Valence (chemistry)","level":2,"score":0.328000009059906},{"id":"https://openalex.org/C68913812","wikidata":"https://www.wikidata.org/wiki/Q238156","display_name":"Coordination complex","level":3,"score":0.3140000104904175},{"id":"https://openalex.org/C30095370","wikidata":"https://www.wikidata.org/wiki/Q899488","display_name":"Protonation","level":3,"score":0.305400013923645},{"id":"https://openalex.org/C71240020","wikidata":"https://www.wikidata.org/wiki/Q186011","display_name":"Stereochemistry","level":1,"score":0.2842000126838684},{"id":"https://openalex.org/C2781442258","wikidata":"https://www.wikidata.org/wiki/Q46310","display_name":"Ab initio","level":2,"score":0.2815000116825104},{"id":"https://openalex.org/C130188946","wikidata":"https://www.wikidata.org/wiki/Q4391470","display_name":"Natural bond orbital","level":3,"score":0.28110000491142273},{"id":"https://openalex.org/C135889238","wikidata":"https://www.wikidata.org/wiki/Q46276","display_name":"Kinetic energy","level":2,"score":0.28029999136924744},{"id":"https://openalex.org/C2776568683","wikidata":"https://www.wikidata.org/wiki/Q23005640","display_name":"Moiety","level":2,"score":0.27639999985694885},{"id":"https://openalex.org/C86025842","wikidata":"https://www.wikidata.org/wiki/Q5358432","display_name":"Electronic structure","level":2,"score":0.27399998903274536},{"id":"https://openalex.org/C8010536","wikidata":"https://www.wikidata.org/wiki/Q160398","display_name":"Crystallography","level":1,"score":0.2637999951839447},{"id":"https://openalex.org/C106773901","wikidata":"https://www.wikidata.org/wiki/Q19588","display_name":"Transition metal","level":3,"score":0.2599000036716461},{"id":"https://openalex.org/C32909587","wikidata":"https://www.wikidata.org/wiki/Q11369","display_name":"Molecule","level":2,"score":0.25429999828338623},{"id":"https://openalex.org/C74080474","wikidata":"https://www.wikidata.org/wiki/Q7305975","display_name":"Redistribution (election)","level":3,"score":0.2506999969482422},{"id":"https://openalex.org/C41339378","wikidata":"https://www.wikidata.org/wiki/Q3720155","display_name":"Electronic effect","level":3,"score":0.2502000033855438}],"mesh":[],"locations_count":1,"locations":[{"id":"doi:10.26434/chemrxiv.15010004/v1","doi":"https://doi.org/10.26434/chemrxiv.15010004/v1","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.15010004/v1","pdf_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010004/v1","source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by","license_id":"https://openalex.org/licenses/cc-by","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"}],"best_oa_location":{"id":"doi:10.26434/chemrxiv.15010004/v1","doi":"https://doi.org/10.26434/chemrxiv.15010004/v1","is_oa":true,"landing_page_url":"https://doi.org/10.26434/chemrxiv.15010004/v1","pdf_url":"https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010004/v1","source":{"id":"https://openalex.org/S4393918830","display_name":"ChemRxiv","issn_l":"2573-2293","issn":["2573-2293"],"is_oa":false,"is_in_doaj":false,"is_core":false,"listed_in":[],"host_organization":null,"host_organization_name":null,"host_organization_lineage":[],"host_organization_lineage_names":[],"type":"repository"},"license":"cc-by","license_id":"https://openalex.org/licenses/cc-by","version":"acceptedVersion","is_accepted":true,"is_published":false,"raw_source_name":null,"raw_type":"posted-content"},"sustainable_development_goals":[],"study_designs":[],"awards":[],"funders":[],"has_content":{"pdf":true,"grobid_xml":true},"content_urls":{"pdf":"https://content.openalex.org/works/W7220834908.pdf","grobid_xml":"https://content.openalex.org/works/W7220834908.grobid-xml"},"referenced_works_count":0,"referenced_works":[],"related_works":["https://openalex.org/W4407940543","https://openalex.org/W2989570082","https://openalex.org/W1735301566","https://openalex.org/W3042867955","https://openalex.org/W1991653595","https://openalex.org/W2360228688","https://openalex.org/W1970416797","https://openalex.org/W2087111826","https://openalex.org/W7160242397","https://openalex.org/W2112749195"],"abstract_inverted_index":{"Metal":[0],"coordination":[1,61,74],"provides":[2],"an":[3],"effective":[4],"strategy":[5],"for":[6,105],"modulating":[7],"the":[8,27,69,110,139,168,190],"acidity":[9,39,185],"of":[10,29,47,113,130,146,193],"otherwise":[11],"weak":[12],"C\u2013H":[13],"bonds":[14],"and":[15,34,54,63,86,107,116,179,186],"controlling":[16],"proton-transfer":[17,187],"reactivity.":[18],"Herein,":[19],"we":[20],"use":[21],"density":[22],"functional":[23],"theory":[24],"to":[25,67,195],"investigate":[26],"effects":[28,181],"metal":[30,175],"identity,":[31,176],"tautomeric":[32,64,127,177],"state,":[33],"substituent":[35,180],"electronics":[36],"on":[37,126],"\u03b1-hydrogen":[38,197],"in":[40,199],"metal-coordinated":[41],"keto\u2013enol":[42,200],"systems.":[43,201],"A":[44],"systematic":[45],"set":[46],"approximately":[48,147],"128":[49],"Au(III)-coordinated":[50,131],"structures":[51,133,142],"containing":[52],"electron-donating":[53,98],"electron-withdrawing":[55],"substituents":[56,93],"was":[57],"examined,":[58],"with":[59,79,153,163],"multiple":[60],"geometries":[62],"forms":[65],"considered":[66],"identify":[68],"thermodynamically":[70],"preferred":[71],"states.":[72],"Au(III)":[73,194],"substantially":[75,158],"enhances":[76],"\u03b1-C\u2013H":[77,184],"acidity,":[78,96],"many":[80],"systems":[81],"exhibiting":[82],"highly":[83],"favorable":[84],"deprotonation":[85,129],"strongly":[87],"acidic":[88],"computed":[89],"pKa":[90],"values.":[91],"Electron-withdrawing":[92],"generally":[94],"increase":[95],"whereas":[97,138],"groups":[99],"reduce":[100],"it,":[101],"although":[102],"deviations":[103],"observed":[104],"OMe":[106],"CF3":[108],"highlight":[109],"additional":[111],"roles":[112],"charge":[114],"delocalization":[115],"electrostatic":[117],"stabilization.":[118],"Kinetic":[119],"analysis":[120],"further":[121],"reveals":[122],"a":[123],"strong":[124],"dependence":[125],"state:":[128],"enol":[132],"proceeds":[134],"through":[135],"barrierless":[136],"pathways,":[137],"corresponding":[140],"keto":[141,169],"require":[143],"activation":[144],"barriers":[145],"37\u201346":[148],"kcal":[149],"mol\u22121.":[150],"Comparative":[151],"calculations":[152],"Co(III)-and":[154],"Rh(III)-porphyrin":[155],"complexes":[156],"show":[157],"weaker":[159],"acidification":[160,198],"than":[161],"Au(III),":[162],"both":[164],"metals":[165],"preferentially":[166],"stabilizing":[167],"tautomer.":[170],"These":[171],"results":[172],"demonstrate":[173],"that":[174],"structure,":[178],"collectively":[182],"govern":[183],"reactivity,":[188],"highlighting":[189],"distinctive":[191],"ability":[192],"promote":[196]},"counts_by_year":[],"updated_date":"2026-10-28T10:33:24.094632","created_date":"2026-10-08T00:00:00"}