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This study provides a systematic assessment of the catalytic reactivity of recently reported intra-molecular FLPs on the activation of typical inert C-H bonds, including 1-methylpyrrole, methane, benzyl, propylene, and benzene, in terms of density functional theory (DFT) calculations. The reactivity of FLPs is evaluated according to the calculated reaction thermodynamic and energy barriers of C-H bond activation processes in the framework of concerted C-H activation mechanisms. As for 1-methylpyrrole, 14 types of N-B-based and 15 types of P-B-based FLPs are proposed to be active. Although none of the evaluated FLPs are able to catalyze the C-H activation of methane, benzyl, or propylene, four types of N-B-based FLPs are suggested to be capable of catalyzing the activation of benzene. Moreover, the influence of the strength of Lewis acid (LA) and Lewis base (LB), and the differences between the influences of LA and LB on the catalytic reactivity of FLPs, are also discussed briefly. This systematic assessment of the catalytic activity of FLPs should provide valuable guidelines to aid the development of efficient FLP-based metal-free catalysts for C-H bond activation.<\/jats:p>","DOI":"10.3390\/molecules29010024","type":"journal-article","created":{"date-parts":[[2023,12,19]],"date-time":"2023-12-19T11:17:24Z","timestamp":1702984644000},"page":"24","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Systematic Assessment of the Catalytic Reactivity of Frustrated Lewis Pairs in C-H Bond Activation"],"prefix":"10.3390","volume":"29","author":[{"given":"Yongjie","family":"Guo","sequence":"first","affiliation":[{"name":"Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xueqi","family":"Lian","sequence":"additional","affiliation":[{"name":"Key Laboratory of Electronic Functional Materials and Devices of Guangdong Province, School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516007, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hao","family":"Zhang","sequence":"additional","affiliation":[{"name":"Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xueling","family":"Zhang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Electronic Functional Materials and Devices of Guangdong Province, School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516007, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jun","family":"Chen","sequence":"additional","affiliation":[{"name":"Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Changzhong","family":"Chen","sequence":"additional","affiliation":[{"name":"Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5301-069X","authenticated-orcid":false,"given":"Xiaobing","family":"Lan","sequence":"additional","affiliation":[{"name":"Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Youxiang","family":"Shao","sequence":"additional","affiliation":[{"name":"Key Laboratory of Electronic Functional Materials and Devices of Guangdong Province, School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516007, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,12,19]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1038\/nature08634","article-title":"Main-group elements as transition metals","volume":"463","author":"Power","year":"2010","journal-title":"Nature"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"12232","DOI":"10.1021\/ja053247a","article-title":"Facile Activation of Dihydrogen by an Unsaturated Heavier Main Group Compound","volume":"127","author":"Spikes","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"439","DOI":"10.1126\/science.1141474","article-title":"Facile Splitting of Hydrogen and Ammonia by Nucleophilic Activation at a Single Carbon Center","volume":"316","author":"Frey","year":"2007","journal-title":"Science"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"20002","DOI":"10.1021\/jacs.1c10845","article-title":"Diverse Uses of the Reaction of Frustrated Lewis Pair (FLP) with Hydrogen","volume":"143","author":"Stephan","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"aaf7229","DOI":"10.1126\/science.aaf7229","article-title":"The broadening reach of frustrated Lewis pair chemistry","volume":"354","author":"Stephan","year":"2016","journal-title":"Science"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"6400","DOI":"10.1002\/anie.201409800","article-title":"Frustrated Lewis Pair Chemistry: Development and Perspectives","volume":"54","author":"Stephan","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"10018","DOI":"10.1021\/jacs.5b06794","article-title":"Frustrated Lewis Pairs","volume":"137","author":"Stephan","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1124","DOI":"10.1126\/science.1134230","article-title":"Reversible, Metal-Free Hydrogen Activation","volume":"314","author":"Welch","year":"2006","journal-title":"Science"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"3212","DOI":"10.1002\/anie.201511048","article-title":"A P\u2212H Functionalized Al\/P Frustrated Lewis Pair: Substrate Activation and Selective Hydrogen Transfer","volume":"55","author":"Keweloh","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1212","DOI":"10.1021\/om4012246","article-title":"Al\/P-Based Frustrated Lewis Pairs: Limitations of Their Synthesis by Hydroalumination and Formation of Dialkylaluminum Hydride Adducts","volume":"33","author":"Uhl","year":"2014","journal-title":"Organometallics"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"5008","DOI":"10.1021\/om400620h","article-title":"Reactions of an Al\u2013P-Based Frustrated Lewis Pair with Carbonyl Compounds: Dynamic Coordination of Benzaldehyde, Activation of Benzoyl Chloride, and Al\u2013C Bond Cleavage with Benzamide","volume":"32","author":"Uhl","year":"2013","journal-title":"Organometallics"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"4256","DOI":"10.1002\/anie.201208746","article-title":"Reaction of a P\/Al-Based Frustrated Lewis Pair with Ammonia, Borane, and Amine\u2013Boranes: Adduct Formation and Catalytic Dehydrogenation","volume":"52","author":"Appelt","year":"2013","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Erker, G., and Stephan, D.W. (2013). Frustrated Lewis Pairs II: Expanding the Scope, Springer.","DOI":"10.1007\/978-3-642-37759-4"},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Erker, G., and Stephan, D.W. (2013). Frustrated Lewis Pairs II: Expanding the Scope, Springer.","DOI":"10.1007\/978-3-642-37759-4"},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Wan, Q., Lin, S., and Guo, H. (2022). Frustrated Lewis Pairs in Heterogeneous Catalysis: Theoretical Insights. Molecules, 27.","DOI":"10.3390\/molecules27123734"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"5541","DOI":"10.1039\/C7CS00691H","article-title":"Semi-solid and solid frustrated Lewis pair catalysts","volume":"47","author":"Ma","year":"2018","journal-title":"Chem. Soc. Rev."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"e202201236","DOI":"10.1002\/asia.202201236","article-title":"Screening Carbon-Boron Frustrated Lewis Pairs for Small-Molecule Activation including N2, O2, CO, CO2, CS2, H2O and CH4: A Computational Study","volume":"18","author":"Zeng","year":"2023","journal-title":"Chem. Asian J."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"13149","DOI":"10.1021\/acs.inorgchem.2c01902","article-title":"Activation of H\u2013H, HO\u2013H, C(sp2)\u2013H, C(sp3)\u2013H, and RO\u2013H Bonds by Transition-Metal Frustrated Lewis Pairs Based on M\/N (M = Rh, Ir) Couples","volume":"61","author":"Carmona","year":"2022","journal-title":"Inorg. Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"11902","DOI":"10.3390\/molecules200711902","article-title":"Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide","volume":"20","author":"Rochette","year":"2015","journal-title":"Molecules"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2870","DOI":"10.1021\/acs.organomet.7b00346","article-title":"Frustrated Lewis Pair Catalyzed S\u2013H Bond Borylation","volume":"36","author":"Rochette","year":"2017","journal-title":"Organometallics"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"12418","DOI":"10.1002\/anie.201307254","article-title":"Frustrated Lewis Pair Catalyzed Hydroamination of Terminal Alkynes","volume":"52","author":"Mahdi","year":"2013","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"7433","DOI":"10.1002\/anie.200802596","article-title":"Hydrogen and Amine Activation by a Frustrated Lewis Pair of a Bulky N-Heterocyclic Carbene and B(C6F5)3","volume":"47","author":"Chase","year":"2008","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"23476","DOI":"10.1002\/anie.202008798","article-title":"Frustrated Lewis Pairs Comprising Nitrogen Lewis Acids for Si\u2013H Bond Activation","volume":"59","author":"Avigdori","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"6940","DOI":"10.1021\/jacs.6b03443","article-title":"The Asymmetric Piers Hydrosilylation","volume":"138","author":"Hermeke","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"2513","DOI":"10.1021\/acscatal.5b00189","article-title":"Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine\u2013Borane Catalysts: On the Role of the Formaldehyde Adduct","volume":"5","author":"Declercq","year":"2015","journal-title":"ACS Catal."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"9326","DOI":"10.1021\/ja404585p","article-title":"A Highly Active Phosphine\u2013Borane Organocatalyst for the Reduction of CO2 to Methanol Using Hydroboranes","volume":"135","author":"Courtemanche","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Pal, R., Ghara, M., and Chattaraj, P.K. (2022). Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs. Catalysts, 12.","DOI":"10.3390\/catal12020201"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"124","DOI":"10.1016\/j.ccr.2016.05.005","article-title":"Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles","volume":"334","author":"Fontaine","year":"2017","journal-title":"Coord. Chem. Rev."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"6757","DOI":"10.1002\/anie.202014562","article-title":"Alkyne 1,1-Hydroboration to a Reactive Frustrated P\/B-H Lewis Pair","volume":"60","author":"Daniliuc","year":"2021","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"718","DOI":"10.1038\/nchem.1693","article-title":"A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes","volume":"5","author":"Chernichenko","year":"2013","journal-title":"Nat. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"3925","DOI":"10.1002\/anie.201006901","article-title":"Geminal Phosphorus\/Aluminum-Based Frustrated Lewis Pairs: C-H versus C-C Activation and CO2 Fixation","volume":"50","author":"Appelt","year":"2011","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"125","DOI":"10.1021\/om9008636","article-title":"Activation of Terminal Alkynes by Frustrated Lewis Pairs","volume":"29","author":"Jiang","year":"2010","journal-title":"Organometallics"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"2286","DOI":"10.1021\/acscatal.2c05995","article-title":"Understanding and Expanding Zinc Cation\/Amine Frustrated Lewis Pair Catalyzed C\u2013H Borylation","volume":"13","author":"Grundy","year":"2023","journal-title":"ACS Catal."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"5387","DOI":"10.1039\/C6CC01267A","article-title":"Bench-stable frustrated Lewis pair chemistry: Fluoroborate salts as precatalysts for the C\u2013H borylation of heteroarenes","volume":"52","author":"Rochette","year":"2016","journal-title":"Chem. Commun."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"4860","DOI":"10.1021\/jacs.6b00819","article-title":"Metal-Free sp2-C\u2013H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes","volume":"138","author":"Chernichenko","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"513","DOI":"10.1126\/science.aab3591","article-title":"Metal-free catalytic C-H bond activation and borylation of heteroarenes","volume":"349","author":"Courtemanche","year":"2015","journal-title":"Science"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"473","DOI":"10.1126\/science.aac9244","article-title":"A leap ahead for activating C-H bonds","volume":"349","author":"Bose","year":"2015","journal-title":"Science"},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Zhou, Y., Chen, Y., Luo, X., and Wang, X. (2023). Nonoxidative Coupling of Methane to Produce C2 Hydrocarbons on FLPs of an Albite Surface. Molecules, 28.","DOI":"10.3390\/molecules28031037"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"19230","DOI":"10.1039\/C6DT04206F","article-title":"Indirect synthesis of a pair of formal methane activation products at a phosphane\/borane frustrated Lewis pair","volume":"45","author":"Daniliuc","year":"2016","journal-title":"Dalton Trans."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"20056","DOI":"10.1021\/ja208093c","article-title":"N-Directed Aliphatic C\u2013H Borylation Using Borenium Cation Equivalents","volume":"133","author":"Prokofjevs","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"3567","DOI":"10.1002\/chem.201700390","article-title":"Frustrated Lewis Pair Mediated Csp3\u2212H Activation","volume":"23","author":"Rochette","year":"2017","journal-title":"Chem. Eur. J."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"10701","DOI":"10.1021\/ja903878z","article-title":"Rationalizing the Reactivity of Frustrated Lewis Pairs: Thermodynamics of H2 Activation and the Role of Acid\u2212Base Properties","volume":"131","author":"Rokob","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"12268","DOI":"10.1002\/anie.201706226","article-title":"Group 6 Transition-Metal\/Boron Frustrated Lewis Pair Templates Activate N2 and Allow its Facile Borylation and Silylation","volume":"56","author":"Simonneau","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"2944","DOI":"10.1021\/jacs.7b00491","article-title":"Dihydrogen and Acetylene Activation by a Gold(I)\/Platinum(0) Transition Metal Only Frustrated Lewis Pair","volume":"139","author":"Campos","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1017","DOI":"10.1021\/acs.inorgchem.5b01424","article-title":"Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs","volume":"55","author":"Chapman","year":"2016","journal-title":"Inorg. Chem."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"2223","DOI":"10.1002\/anie.201409872","article-title":"Cooperative Lewis Pairs Based on Late Transition Metals: Activation of Small Molecules by Platinum(0) and B(C6F5)3","volume":"54","author":"Forrest","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"9653","DOI":"10.1021\/acs.chemrev.3c00217","article-title":"Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor\u2013Acceptor Systems in Main Group Chemistry","volume":"123","author":"Pahar","year":"2023","journal-title":"Chem. Rev."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"3454","DOI":"10.1039\/C8CS00940F","article-title":"Radicals derived from Lewis acid\/base pairs","volume":"48","author":"Liu","year":"2019","journal-title":"Chem. Soc. Rev."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"259","DOI":"10.1016\/j.chempr.2017.05.022","article-title":"A Radical Mechanism for Frustrated Lewis Pair Reactivity","volume":"3","author":"Liu","year":"2017","journal-title":"Chem"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"12227","DOI":"10.1021\/jacs.5b08614","article-title":"Facile Reversibility by Design: Tuning Small Molecule Capture and Activation by Single Component Frustrated Lewis Pairs","volume":"137","author":"Mo","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"1102","DOI":"10.1021\/acs.orglett.8b00024","article-title":"Frustrated Lewis Pair Catalyzed C\u2013H Activation of Heteroarenes: A Stepwise Carbene Mechanism Due to Distance Effect","volume":"20","author":"Shao","year":"2018","journal-title":"Org. Lett."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"15826","DOI":"10.1002\/chem.201603597","article-title":"Understanding the Subtleties of Frustrated Lewis Pair Activation of Carbonyl Compounds by N-Heterocyclic Carbene\/Alkyl Gallium Pairings","volume":"22","author":"Uzelac","year":"2016","journal-title":"Chem. Eur. J."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"413","DOI":"10.1063\/1.556018","article-title":"Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update","volume":"27","author":"Hunter","year":"1998","journal-title":"J. Phys. Chem. Ref. Data"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"1685","DOI":"10.1021\/om049091p","article-title":"From B(C6F5)3 to B(OC6F5)3:\u2009 Synthesis of (C6F5)2BOC6F5 and C6F5B(OC6F5)2 and Their Relative Lewis Acidity","volume":"24","author":"Britovsek","year":"2005","journal-title":"Organometallics"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"4629","DOI":"10.1016\/0032-3861(96)00323-0","article-title":"A convenient n.m.r. method for the measurement of Lewis acidity at boron centres: Correlation of reaction rates of Lewis acid initiated epoxide polymerizations with Lewis acidity","volume":"37","author":"Beckett","year":"1996","journal-title":"Polymer"},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"207","DOI":"10.1016\/S0010-8545(00)80274-X","article-title":"Empirical approach to molecular interactions","volume":"15","author":"Gutmann","year":"1975","journal-title":"Coord. Chem. Rev."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"5689","DOI":"10.1039\/C7CS00154A","article-title":"Designing effective \u2018frustrated Lewis pair\u2019 hydrogenation catalysts","volume":"46","author":"Scott","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"1350074","DOI":"10.1142\/S0219633613500740","article-title":"Assessing the performance of commonly used DFT functionals in studying the chemistry of frustrated Lewis pairs","volume":"13","author":"Huang","year":"2014","journal-title":"J. Theor. Comput. Chem."},{"key":"ref_59","doi-asserted-by":"crossref","unstructured":"Erker, G., and Stephan, D.W. (2013). Frustrated Lewis Pairs I: Uncovering and Understanding, Springer.","DOI":"10.1007\/978-3-642-36697-0"},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"e202205735","DOI":"10.1002\/anie.202205735","article-title":"Best-Practice DFT Protocols for Basic Molecular Computational Chemistry**","volume":"61","author":"Bursch","year":"2022","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"12590","DOI":"10.1021\/jp408166m","article-title":"Performance of M06, M06-2X, and M06-HF Density Functionals for Conformationally Flexible Anionic Clusters: M06 Functionals Perform Better than B3LYP for a Model System with Dispersion and Ionic Hydrogen-Bonding Interactions","volume":"117","author":"Walker","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"5121","DOI":"10.1021\/jp060231d","article-title":"Comparative DFT Study of van der Waals Complexes:\u2009 Rare-Gas Dimers, Alkaline-Earth Dimers, Zinc Dimer, and Zinc-Rare-Gas Dimers","volume":"110","author":"Zhao","year":"2006","journal-title":"J. Phys. Chem. A"},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1021\/ct0499783","article-title":"Using Hessian Updating To Increase the Efficiency of a Hessian Based Predictor-Corrector Reaction Path Following Method","volume":"1","author":"Hratchian","year":"2005","journal-title":"J. Chem. Theory Comput."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"9918","DOI":"10.1063\/1.1724823","article-title":"Accurate reaction paths using a Hessian based predictor\u2013corrector integrator","volume":"120","author":"Hratchian","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"363","DOI":"10.1021\/ar00072a001","article-title":"The path of chemical reactions\u2014The IRC approach","volume":"14","author":"Fukui","year":"1981","journal-title":"Acc. Chem. Res."},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"1655","DOI":"10.1021\/acscatal.5b02395","article-title":"General H2 Activation Modes for Lewis Acid\u2013Transition Metal Bifunctional Catalysts","volume":"6","author":"Li","year":"2016","journal-title":"ACS Catal."},{"key":"ref_68","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. (2010). Gaussian 09, Revision B.01, Gaussian, Inc."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"1749","DOI":"10.1002\/anie.201410141","article-title":"Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H2 Addition and Kinetic Analysis","volume":"54","author":"Chernichenko","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"9029","DOI":"10.1039\/c2dt30926b","article-title":"Hydrogen activation by 2-boryl-N,N-dialkylanilines: A revision of Piers\u2019 ansa-aminoborane","volume":"41","author":"Chernichenko","year":"2012","journal-title":"Dalton Trans."},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"18340","DOI":"10.1039\/C5DT02659H","article-title":"Naphthylaminoborane: From structural switches to frustrated Lewis pair reactivity","volume":"44","author":"Pla","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"6745","DOI":"10.1021\/om4004225","article-title":"An Enamine\/HB(C6F5)2 Adduct as a Dormant State in Frustrated Lewis Pair Chemistry","volume":"32","author":"Xu","year":"2013","journal-title":"Organometallics"},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"1842","DOI":"10.1039\/c1sc00124h","article-title":"Intramolecular frustrated N\/B lewis pairs by enamine hydroboration","volume":"2","author":"Schwendemann","year":"2011","journal-title":"Chem. Sci."},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"212","DOI":"10.1002\/asia.201200776","article-title":"Reaction of an \u201cInvisible\u201d Frustrated N\/B Lewis Pair with Dihydrogen","volume":"8","author":"Schwendemann","year":"2013","journal-title":"Chem. Asian J."},{"key":"ref_75","doi-asserted-by":"crossref","first-page":"10412","DOI":"10.1002\/chem.201300462","article-title":"Frustrated Lewis Pair Chemistry of Chiral (+)-Camphor-Based Aminoboranes","volume":"19","author":"Lindqvist","year":"2013","journal-title":"Chem. Eur. J."},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"14117","DOI":"10.1021\/ja806627s","article-title":"Molecular Tweezers for Hydrogen: Synthesis, Characterization, and Reactivity","volume":"130","author":"Sumerin","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"2093","DOI":"10.1002\/adsc.201100206","article-title":"Highly Active Metal-Free Catalysts for Hydrogenation of Unsaturated Nitrogen-Containing Compounds","volume":"353","author":"Sumerin","year":"2011","journal-title":"Adv. Synth. Catal."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"6186","DOI":"10.1002\/anie.201000520","article-title":"Reaction of Singlet Dioxygen with Phosphine\u2013Borane Derivatives: From Transient Phosphine Peroxides to Crystalline Peroxoboronates","volume":"49","author":"Porcel","year":"2010","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"4236","DOI":"10.1021\/ja210160k","article-title":"New Insights into Frustrated Lewis Pairs: Structural Investigations of Intramolecular Phosphane\u2013Borane Adducts by Using Modern Solid-State NMR Techniques and DFT Calculations","volume":"134","author":"Wiegand","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"709","DOI":"10.1039\/C2DT31737K","article-title":"Functional group chemistry at intramolecular frustrated Lewis pairs: Substituent exchange at the Lewis acid site with 9-BBN","volume":"42","author":"Erdmann","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_81","doi-asserted-by":"crossref","unstructured":"Spies, P., Erker, G., Kehr, G., Bergander, K., Fr\u00f6hlich, R., Grimme, S., and Stephan, D.W. (2007). Rapid intramolecular heterolytic dihydrogen activation by a four-membered heterocyclic phosphane\u2013borane adduct. Chem. Commun., 5072\u20135074.","DOI":"10.1039\/b710475h"},{"key":"ref_82","doi-asserted-by":"crossref","unstructured":"Spies, P., Kehr, G., Bergander, K., Wibbeling, B., Fr\u00f6hlich, R., and Erker, G. (2009). Metal-free dihydrogen activation chemistry: Structural and dynamic features of intramolecular P\/B pairs. Dalton Trans., 1534\u20131541.","DOI":"10.1039\/b815832k"},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"8882","DOI":"10.1021\/ja400338e","article-title":"Noninteracting, Vicinal Frustrated P\/B-Lewis Pair at the Norbornane Framework: Synthesis, Characterization, and Reactions","volume":"135","author":"Sajid","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_84","doi-asserted-by":"crossref","first-page":"201","DOI":"10.1021\/ja210214r","article-title":"Preorganized Frustrated Lewis Pairs","volume":"134","author":"Bertini","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"ref_85","doi-asserted-by":"crossref","first-page":"3293","DOI":"10.1021\/ja413060u","article-title":"Internal Adduct Formation of Active Intramolecular C4-bridged Frustrated Phosphane\/Borane Lewis Pairs","volume":"136","author":"Wang","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_86","doi-asserted-by":"crossref","first-page":"14069","DOI":"10.1002\/chem.201001814","article-title":"Structure and Dynamic Features of an Intramolecular Frustrated Lewis Pair","volume":"16","author":"Axenov","year":"2010","journal-title":"Chem. Eur. J."},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1002\/chem.200700649","article-title":"Structural Importance of Secondary Interactions in Molecules: Origin of Unconventional Conformations of Phosphine\u2013Borane Adducts","volume":"14","author":"Spies","year":"2008","journal-title":"Chem. Eur. J."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"4288","DOI":"10.1039\/c1cc10241a","article-title":"Chemistry of a geminal frustrated Lewis pair featuring electron withdrawing C6F5 substituents at both phosphorus and boron","volume":"47","author":"Stute","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_89","doi-asserted-by":"crossref","first-page":"4211","DOI":"10.1021\/om200569k","article-title":"Electronic Control of Frustrated Lewis Pair Behavior: Chemistry of a Geminal Alkylidene-Bridged Per-pentafluorophenylated P\/B Pair","volume":"30","author":"Rosorius","year":"2011","journal-title":"Organometallics"},{"key":"ref_90","doi-asserted-by":"crossref","first-page":"9014","DOI":"10.1021\/ja5028293","article-title":"Frustrated Lewis Pair Modification by 1,1-Carboboration: Disclosure of a Phosphine Oxide Triggered Nitrogen Monoxide Addition to an Intramolecular P\/B Frustrated Lewis Pair","volume":"136","author":"Liedtke","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_91","doi-asserted-by":"crossref","first-page":"4487","DOI":"10.1039\/c2dt32806b","article-title":"Electronic control in frustrated Lewis pair chemistry: Adduct formation of intramolecular FLP systems with \u2013P(C6F5)2 Lewis base components","volume":"42","author":"Stute","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_92","doi-asserted-by":"crossref","first-page":"4610","DOI":"10.1021\/ja1110283","article-title":"P\u2212C Bond Activation Chemistry: Evidence for 1,1-Carboboration Reactions Proceeding with Phosphorus\u2212Carbon Bond Cleavage","volume":"133","author":"Ekkert","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_93","doi-asserted-by":"crossref","first-page":"11881","DOI":"10.1021\/ic401406k","article-title":"Peri-Substituted (Ace)Naphthylphosphinoboranes. (Frustrated) Lewis Pairs","volume":"52","author":"Beckmann","year":"2013","journal-title":"Inorg. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/1\/24\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T21:41:41Z","timestamp":1760132501000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/1\/24"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,12,19]]},"references-count":93,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2024,1]]}},"alternative-id":["molecules29010024"],"URL":"https:\/\/doi.org\/10.3390\/molecules29010024","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,12,19]]}}}