{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,22]],"date-time":"2026-07-22T21:05:50Z","timestamp":1784754350684,"version":"3.55.0"},"reference-count":30,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2020,6,17]],"date-time":"2020-06-17T00:00:00Z","timestamp":1592352000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000928","name":"Welch Foundation","doi-asserted-by":"publisher","award":["B-1985-20190330"],"award-info":[{"award-number":["B-1985-20190330"]}],"id":[{"id":"10.13039\/100000928","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>In the present density functional theory (DFT) research, nine different molecules, each with different combinations of A (triel) and E (divalent metal) elements, were reacted to effect methane C\u2013H activation. The compounds modeled herein incorporated the triels A = B, Al, or Ga and the divalent metals E = Be, Mg, or Zn. The results show that changes in the divalent metal have a much bigger impact on the thermodynamics and methane activation barriers than changes in the triels. The activating molecules that contained beryllium were most likely to have the potential for activating methane, as their free energies of reaction and free energy barriers were close to reasonable experimental values (i.e., \u0394G close to thermoneutral, \u0394G\u2021 ~30 kcal\/mol). In contrast, the molecules that contained larger elements such as Zn and Ga had much higher \u0394G\u2021. The addition of various substituents to the A\u2013E complexes did not seem to affect thermodynamics but had some effect on the kinetics when substituted closer to the active site.<\/jats:p>","DOI":"10.3390\/molecules25122794","type":"journal-article","created":{"date-parts":[[2020,6,18]],"date-time":"2020-06-18T12:21:46Z","timestamp":1592482906000},"page":"2794","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Computational Study of Methane C\u2013H Activation by Main Group and Mixed Main Group\u2013Transition Metal Complexes"],"prefix":"10.3390","volume":"25","author":[{"given":"Carly C.","family":"Carter","sequence":"first","affiliation":[{"name":"Center of Advanced Scientific Computing and Modeling, Department of Chemistry, University of North Texas, Denton, TX 76201, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Thomas R.","family":"Cundari","sequence":"additional","affiliation":[{"name":"Center of Advanced Scientific Computing and Modeling, Department of Chemistry, University of North Texas, Denton, TX 76201, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,6,17]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"507","DOI":"10.1038\/417507a","article-title":"Understanding and exploiting C-H bond activation","volume":"417","author":"Labinger","year":"2002","journal-title":"Nature"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"391","DOI":"10.1038\/446391a","article-title":"C-H activation","volume":"446","author":"Bergman","year":"2007","journal-title":"Nature"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"248","DOI":"10.5155\/eurjchem.7.2.248-270.1412","article-title":"Recent advance in direct sp3 carbon-hydrogen bond functionalizations","volume":"7","author":"Cai","year":"2016","journal-title":"Eur. J. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"16646","DOI":"10.1039\/c3dt52164h","article-title":"Activation of carbon-hydrogen bonds and dihydrogen by 1,2-CH-addition across metal-heteroatom bonds","volume":"42","author":"Webb","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"2879","DOI":"10.1021\/cr9411886","article-title":"Activation of C-H bonds by metal complexes","volume":"97","author":"Shilov","year":"1997","journal-title":"Chem. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1021\/ar000209h","article-title":"Catalytic functionalization of arenes and alkanes via C-H bond activation","volume":"34","author":"Jia","year":"2001","journal-title":"Acc. Chem. Res."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2471","DOI":"10.1021\/cr030710y","article-title":"Mechanistic aspects of C-H activation by Pt complexes","volume":"105","author":"Lersch","year":"2005","journal-title":"Chem. Rev."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2495","DOI":"10.1021\/acs.accounts.5b00385","article-title":"Getting down to earth: The renaissance of catalysis with abundant metals","volume":"48","author":"Chirik","year":"2015","journal-title":"Acc. Chem. Res."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"794","DOI":"10.1126\/science.1183281","article-title":"Radical ligands confer nobility on base-metal catalysts","volume":"327","author":"Chirik","year":"2010","journal-title":"Science"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"12282","DOI":"10.1021\/acs.inorgchem.7b01736","article-title":"Methane C-H activation via 3D metal methoxide complexes with potentially redox-noninnocent pincer ligands: A density functional theory study","volume":"56","author":"Najafian","year":"2017","journal-title":"Inorg. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"11539","DOI":"10.1039\/C6CP00505E","article-title":"Methane activation by metal-free Lewis acid centers only\u2014A computational design and mechanism study","volume":"18","author":"Ma","year":"2016","journal-title":"Phys. Chem. Phys. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"10018","DOI":"10.1021\/jacs.5b06794","article-title":"Frustrated Lewis pairs","volume":"32","author":"Stephan","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3841","DOI":"10.1039\/C4CC00697F","article-title":"Heavy metal boryl chemistry: Complexes of cadmium mercury and lead","volume":"50","author":"Protchenko","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"737","DOI":"10.1039\/C4CC08519A","article-title":"Beryllium bis(diazaborolyl): Old neighbors finally shake hands","volume":"51","author":"Arnold","year":"2015","journal-title":"Chem. Commun."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"9570","DOI":"10.1021\/ja073037t","article-title":"Synthesis, structure of borylmagnesium, and its reaction with benzaldehyde to form benzoylborane","volume":"31","author":"Yamashita","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"6606","DOI":"10.1002\/anie.200801728","article-title":"Syntheses, structures, and reactivates of borylcopper and -zinc compounds: 1,4-silaboration of an alpha, beta-unsaturated ketone to form a gamma-siloxyallylborane","volume":"47","author":"Kajiwara","year":"2008","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_17","first-page":"171","article-title":"The Cambridge structural database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Cryst."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"3146","DOI":"10.1021\/ic060136j","article-title":"Synthesis, structural characterization, and theoretical studies of complexes of magnesium and calcium with gallium heterocycles","volume":"45","author":"Jones","year":"2006","journal-title":"Inorg. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"4914","DOI":"10.1021\/om1001606","article-title":"Group 2 and 12 metal gallyl complexes containing unsupported Ga-M covalent bonds (M = Mg, CaSr, Ba, Zn, Cd)","volume":"29","author":"Bonello","year":"2010","journal-title":"Organometallics"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Luo, Y.R. (2007). Comprehensive Handbook of Chemical Bond Energies, CRC Press.","DOI":"10.1201\/9781420007282"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1372","DOI":"10.1063\/1.464304","article-title":"A new mixing of Hartree-Fock and local density-functional theories","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"ref_22","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2016). Gaussian 16, Revision A.03, Gaussian, Inc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"503","DOI":"10.1016\/0009-2614(88)85250-3","article-title":"MP2 energy evaluation by direct methods","volume":"153","author":"People","year":"1988","journal-title":"Chem. Phys. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals","volume":"120","author":"Zhao","year":"2007","journal-title":"Theor. Chem. Acc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"6615","DOI":"10.1039\/b810189b","article-title":"Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections","volume":"10","author":"Chai","year":"2008","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"4622","DOI":"10.1021\/ic900347e","article-title":"Noncovalent interactions in a transition-metal triphenylphosphine complex: A density functional case study","volume":"48","author":"Sieffert","year":"2009","journal-title":"Inorg. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"6807","DOI":"10.1021\/acs.inorgchem.7b03212","article-title":"Computational study of methane C-H activation by diiminopyridine nitride\/nitridyl complexes of 3D transition metals and main-group elements","volume":"57","author":"Sun","year":"2018","journal-title":"Inorg. Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"68","DOI":"10.1016\/j.micromeso.2010.09.028","article-title":"A density functional theory study of C\u2013H bond activation of methane on a bridge site of M\u2013O\u2013M-ZSM-5 Clusters (M = Au, Ag, Fe and Cu)","volume":"138","author":"Kurnaz","year":"2011","journal-title":"Micropor. Mesopor. Mater."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"3052","DOI":"10.1039\/B600021E","article-title":"DFT studies of the methyl exchange reaction between Cp2M\u2013CH3 or Cp*2M\u2013CH3 (Cp = C5H5, Cp* = C5Me5, M = Y, Sc, Ln) and CH4. Does M ionic radius control the reaction?","volume":"25","author":"Barros","year":"2006","journal-title":"Dalton Trans."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/12\/2794\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T09:40:05Z","timestamp":1760175605000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/12\/2794"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,6,17]]},"references-count":30,"journal-issue":{"issue":"12","published-online":{"date-parts":[[2020,6]]}},"alternative-id":["molecules25122794"],"URL":"https:\/\/doi.org\/10.3390\/molecules25122794","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,6,17]]}}}