{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T23:48:20Z","timestamp":1790812100236,"version":"4.1.0"},"reference-count":37,"publisher":"Wiley","issue":"44","license":[{"start":{"date-parts":[[2015,9,10]],"date-time":"2015-09-10T00:00:00Z","timestamp":1441843200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"name":"U.S. Department of Energy\u2019s (DOE) Office of Science"},{"name":"Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences, and Geosciences"},{"name":"Molecular Science Computing Facilities in the William\u2005R. Wiley Environmental Molecular Sciences Laboratory"},{"name":"Department of Energy\u2019s Office of Biological and Environmental Research"},{"name":"Pacific Northwest National Laboratory (PNNL)"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2015,10,26]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We report that 2,6\u2010lutidine\u22c5trichloroborane (Lut\u22c5BCl<jats:sub>3<\/jats:sub>) reacts with H<jats:sub>2<\/jats:sub> in toluene, bromobenzene, dichloromethane, and Lut solvents producing the neutral hydride, Lut\u22c5BHCl<jats:sub>2<\/jats:sub>. The mechanism was modeled with density functional theory, and energies of stationary states were calculated at the G3(MP2)B3 level of theory. Lut\u22c5BCl<jats:sub>3<\/jats:sub> was calculated to react with H<jats:sub>2<\/jats:sub> and form the ion pair, [LutH<jats:sup>+<\/jats:sup>][HBCl<jats:sub>3<\/jats:sub><jats:sup>\u2212<\/jats:sup>], with a barrier of \u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup>=24.7\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> (\u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup>=29.8\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>). Metathesis with a second molecule of Lut\u22c5BCl<jats:sub>3<\/jats:sub> produced Lut\u22c5BHCl<jats:sub>2<\/jats:sub> and [LutH<jats:sup>+<\/jats:sup>][BCl<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup>]. The overall reaction is exothermic by 6.0\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> (\u0394<jats:sub>r<\/jats:sub><jats:italic>G<\/jats:italic>\u00b0=\u22121.1). Alternate pathways were explored involving the borenium cation (LutBCl<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup>) and the four\u2010membered boracycle [(CH<jats:sub>2<\/jats:sub>{NC<jats:sub>5<\/jats:sub>H<jats:sub>3<\/jats:sub>Me})BCl<jats:sub>2<\/jats:sub>]. Barriers for addition of H<jats:sub>2<\/jats:sub> across the Lut\/LutBCl<jats:sub>2<\/jats:sub><jats:sup>+<\/jats:sup> pair and the boracycle B\uf8ffC bond are substantially higher (\u0394<jats:italic>G<\/jats:italic><jats:sup><jats:italic>\u2260<\/jats:italic><\/jats:sup>=42.1 and 49.4\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>, respectively), such that these pathways are excluded. The barrier for addition of H<jats:sub>2<\/jats:sub> to the boracycle B\uf8ffN bond is comparable (\u0394<jats:italic>H<\/jats:italic><jats:sup><jats:italic>\u2260<\/jats:italic><\/jats:sup>=28.5 and \u0394<jats:italic>G<\/jats:italic><jats:sup><jats:italic>\u2260<\/jats:italic><\/jats:sup>=32\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>). Conversion of the intermediate 2\u2010(BHCl<jats:sub>2<\/jats:sub>CH<jats:sub>2<\/jats:sub>)\u20106\u2010Me(C<jats:sub>5<\/jats:sub>H<jats:sub>3<\/jats:sub>NH) to Lut\u22c5BHCl<jats:sub>2<\/jats:sub> may occur by intermolecular steps involving proton\/hydride transfers to Lut\/BCl<jats:sub>3<\/jats:sub>. Intramolecular protodeboronation, which could form Lut\u22c5BHCl<jats:sub>2<\/jats:sub> directly, is prohibited by a high barrier (\u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup>=52, \u0394<jats:italic>G<\/jats:italic><jats:sup>\u2260<\/jats:sup>=51\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>).<\/jats:p>","DOI":"10.1002\/chem.201501899","type":"journal-article","created":{"date-parts":[[2015,9,10]],"date-time":"2015-09-10T20:58:40Z","timestamp":1441918720000},"page":"15713-15719","source":"Crossref","is-referenced-by-count":10,"title":["Heterolysis of H<sub>2<\/sub> Across a Classical Lewis Pair, 2,6\u2010Lutidine\u22c5BCl<sub>3<\/sub>: Synthesis, Characterization, and Mechanism"],"prefix":"10.1002","volume":"21","author":[{"given":"Bojana","family":"Ginovska","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tom","family":"Autrey","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kshitij","family":"Parab","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mark E.","family":"Bowden","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert G.","family":"Potter","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Donald M.","family":"Camaioni","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,9,10]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/c2ob25339a"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1dt10152h"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01254a031"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja900572x"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp105000x"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja903878z"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic901726b"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/C2DT31628E"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp3039829"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic901092x"},{"key":"e_1_2_6_12_2","unstructured":"K. Chernichenko PhD thesis University of Helsinki (Helsinki Finland) 2013."},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201410141"},{"key":"e_1_2_6_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201410141"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201203318"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic50202a003"},{"key":"e_1_2_6_16_2","unstructured":"Cambridge Crystallographic Data Center deposition number: CCDC\u20051054650 (2 6\u2010Lutidine\u2010dichloroborane complex) contains the supplementary crystallographic data for this paper. These data are provided free of charge byThe Cambridge Crystallographic Data Centre."},{"key":"e_1_2_6_17_2","unstructured":"\u00a0"},{"key":"e_1_2_6_18_2","first-page":"151","volume":"3","author":"Clayton W. R.","year":"1974","journal-title":"Cryst. Struct. Commun."},{"key":"e_1_2_6_19_2","unstructured":"Cambridge Crystallographic Data Center deposition number: CCDC\u20051208772 (2 6\u2010Lutidine\u2010chloroborane complex) contains crystallographic data for this paper. These data are provided free of charge byThe Cambridge Crystallographic Data Centre."},{"key":"e_1_2_6_20_2","unstructured":"G3(MP2)B3LYP calculations of the [LutBCl2+\u22c5Lut][BCl4\u2212] complex and [Lut\u22c5H2\u22c5BCl2Lut+][BCl4\u2212] TS (Figure\u20054) for H2dissociation could not be performed using the Gaussian\u200598 program. The energies to form these complexes were estimated as follows: G3\u2009MP2 electronic energies of the separated ions were calculated using the GAMESS implementation and corrected using the zero point thermal and entropic contributions calculated at the DFT level of theory. The DFT energies (\u0394H\u00b0298 and \u0394G\u00b0298) to associate the ions was then added to the G3\u2009MP2 energies of the separated ions."},{"key":"e_1_2_6_21_2","unstructured":"See p.\u200518 of the Supporting Information for Ref.\u2005[12]."},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.1693"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1107\/S0108767307043930"},{"key":"e_1_2_6_24_2","unstructured":"\u00a0"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.140.A1133"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRev.136.B864"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20495"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cpc.2010.04.018"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1139\/v92-079"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.478676"},{"key":"e_1_2_6_32_2","unstructured":"M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman V.\u2005G. Zakrzewski J.\u2005J.\u2005A. Montgomery R.\u2005E. Stratmann J.\u2005C. Burant S. Dapprich J.\u2005M. Millam A.\u2005D. Daniels K.\u2005N. Kudin M.\u2005C. Strain O. Farkas J. Tomasi V. Barone M. Cossi R. Cammi B. Mennucci C. Pomelli C. Adamo S. Clifford J. Ochterski G.\u2005A. Petersson P.\u2005Y. Ayala Q. Cui K. Morokuma N. Rega P. Salvador J.\u2005J. Dannenberg D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J. Cioslowski J.\u2005V. Ortiz A.\u2005G. Baboul B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R. Gomperts R.\u2005L. Martin D.\u2005J. Fox T. Keith M.\u2005A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong J.\u2005L. Andres C. Gonzalez M. Head\u2010Gordon E.\u2005S. Replogle J.\u2005A. Pople Gaussian\u200598 Revision\u2005A.11.4 Gaussian Inc. Pittsburgh PA 2002."},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.478385"},{"key":"e_1_2_6_34_2","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540141112"},{"key":"e_1_2_6_36_2","unstructured":"M.\u2005S. Gordon M.\u2005W. Schmidt inTheory and Applications of Computational Chemistry: the first forty years(Eds.: C.\u2005E. Dykstra G. Frenking K.\u2005S. Kim G.\u2005E. 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