Main Group Metal Mediated Hydrogenation Reactions and Catalysis

• Applicant: Professor Dr. Stefan Grimme
• Subject Area: Theoretical Chemistry: Molecules, Materials, Surfaces ; Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2021 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 490737079

• Final Report Year: 2025

Final Report Abstract

Extensive dispersion-corrected DFT calculations are used to understand early main-group metal hydrogenation catalysts. It is shown that: (1) Cooperative Ca-H-Ca bridges rather than reactive terminal Ca-H bond may be involved for catalytic C=C hydrogenation with pressured H2; (2) The observed ring-size effect can be understood mainly by a subtle interplay of solvent, steric and cooperative effects that can be resolved in detail by state-of-the-art quantum chemistry calculations; (3) A novel substrate-dependent catalytic mechanism is disclosed involving cooperative Ca-H-Ca bridges for H2 isotope exchange, competitive Ca-H-Ca bridges and terminal Ca-H bonds for anti-Markovnikov addition of unactivated 1-alkenes, and terminal Ca-H bonds for Markovnikov addition of conjugation-activated styrene; (4) Combined with known hydride bridge-mediated 1-alkene addition and H2 isotope exchange, our mechanism paves a catalytic way to nucleophilic aromatic alkylation and H-isotope exchange reactions that may avoid long-standing problems of multiple alkylation and alkyl isomerization; (5) The double Ae-H-Ae bridged dimer (N"AeH)2 (Ae = Mg, Ca, Sr, Ba) is kinetically more favorable in catalytic hydrogenation with H2, although rate-limited by the initial hydrogenolysis of AeN"2 to form the monomer N"AeH.

Publications

• Acid‐Catalyzed Carbene Transfer from Diazo Compounds: Carbocation versus Carbene as Key Intermediate. European Journal of Organic Chemistry, 2022(17).
  Qu, Zheng‐Wang; Zhu, Hui & Grimme, Stefan
  
• Calcium Hydride Cation Dimer Catalyzed Hydrogenation of Unactivated 1‐Alkenes and H2 Isotope Exchange: Competitive Ca−H−Ca Bridges and Terminal Ca−H Bonds. Chemistry – A European Journal, 29(1).
  Qu, Zheng‐Wang; Zhu, Hui & Grimme, Stefan
  
• Catalyst-free CO2 hydrogenation with BH3NH3 in water: DFT mechanistic insights. Physical Chemistry Chemical Physics, 24(23), 14159-14164.
  Qu, Zheng-Wang; Zhu, Hui; Streubel, Rainer & Grimme, Stefan
  
• Catalytic Isomerization of Unprotected Mesoionic N‐Heterocyclic Olefins and Their Lewis Adducts. European Journal of Organic Chemistry, 2022(35).
  Qu, Zheng‐Wang; Zhu, Hui; Streubel, Rainer & Grimme, Stefan
  
• C−H Deprotonation and C=C Hydrogenation of N‐Heterocyclic Olefin with Calcium Hydride Complexes: Cooperative Ca−H−Ca Bridge versus Terminal Ca−H bond. ChemCatChem, 14(15).
  Qu, Zheng‐Wang; Zhu, Hui; Streubel, Rainer & Grimme, Stefan
  
• Frustrated Lewis pair catalyzed hydrodehalogenation of benzyl-halides. Chemical Communications, 58(8), 1175-1178.
  Wang, Tongtong; Xu, Maotong; Jupp, Andrew R.; Chen, Shi-Ming; Qu, Zheng-Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Intermolecular Carbosilylation of α‐Olefins with C(sp3)−C(sp) Bond Formation Involving Silylium‐Ion Regeneration. Angewandte Chemie International Edition, 61(24).
  He, Tao; Qu, Zheng‐Wang; Klare, Hendrik F. T.; Grimme, Stefan & Oestreich, Martin
  
• Origin of the Ligand Ring‐Size Effect on the Catalytic Activity of Cationic Calcium Hydride Dimers in the Hydrogenation of Unactivated 1‐Alkenes. ChemistryOpen, 11(12).
  Zhu, Hui; Qu, Zheng‐Wang & Grimme, Stefan
  
• Reactions of Diethylazo‐Dicarboxylate with Frustrated Lewis Pairs. Chemistry – A European Journal, 28(53).
  Mandal, Dipendu; Chen, Ting; Qu, Zheng‐Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Reactions of Frustrated Lewis Pairs with Chloro‐Diazirines: Cleavage of N=N Double Bonds. Angewandte Chemie International Edition, 61(37).
  Mandal, Dipendu; Chen, Ting; Qu, Zheng‐Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins. Chemical Science, 13(43), 12696-12702.
  Xin, Tiansi; Geeson, Michael B.; Zhu, Hui; Qu, Zheng-Wang; Grimme, Stefan & Cummins, Christopher C.
  
• The Non‐Ancillary Nature of Trimethylsilylamide Substituents in Boranes and Borinium Cations. Chemistry – A European Journal, 28(27).
  Major, Christopher J.; Qu, Zheng‐Wang; Grimme, Stefan & Stephan, Douglas W.
  
• The Varied Frustrated Lewis Pair Reactivity of the Germylene Phosphaketene (CH{(CMe)(2,6‐iPr2C6H3N)}2)GePCO. Chemistry – A European Journal, 28(25).
  Wu, Yile; Zhao, Zhao; Chen, Ting; Tan, Jingjie; Qu, Zheng‐Wang; Grimme, Stefan; Zhao, Yufen & Stephan, Douglas W.
  
• [4+1] cyclization of α-diazo esters and mesoionic N-heterocyclic olefins. Chemical Communications, 59(32), 4770-4773.
  Liang, Qiuming; Zeng, Yimin; Mendez Ocampo, Pedro A.; Zhu, Hui; Qu, Zheng-Wang; Grimme, Stefan & Song, Datong
  
• A Nuclearity‐Dependent Enantiodivergent Epoxide Opening via Enthalpy‐Controlled Mononuclear and Entropy‐Controlled Dinuclear (Salen)Titanium Catalysis. Angewandte Chemie International Edition, 62(37).
  Li, Shengxiao; Zhu, Hui; Li, Longfei; Chen, Wanjiao; Jiang, Jie; Qu, Zheng‐Wang; Grimme, Stefan & Zhang, Yong‐Qiang
  
• AlCl3-Promoted Intramolecular Indolinone-Quinolone Rearrangement of Spiro[indoline-3,2′-quinoxaline]-2,3′-diones: Easy Access to Quinolino[3,4-b]quinoxalin-6-ones. The Journal of Organic Chemistry, 89(2), 898-917.
  Mamedov, Vakhid A.; Galimullina, Venera R.; Qu, Zheng-Wang; Zhu, Hui; Syakaev, Victor V.; Shamsutdinova, Leisan R.; Sergeev, Mikhail A.; Rizvanov, Il’dar Kh.; Gubaidullin, Aidar T.; Sinyashin, Oleg G. & Grimme, Stefan
  
• Design of transition metal complexes containing a P–E radical motif. Dalton Transactions, 52(8), 2356-2362.
  Zhu, Hui; Qu, Zheng-Wang; Grimme, Stefan; Brehm, Philipp C. & Streubel, Rainer
  
• Diazene Chemistry: Metal-Free Models of N2 Reduction Intermediates. Journal of the American Chemical Society, 145(13), 7101-7106.
  Hussain, Zahid; Luo, Yong-an; Wu, Yile; Qu, Zheng-wang; Grimme, Stefan & Stephan, Douglas W.
  
• Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene‐Based Chiral Hydride Source. Angewandte Chemie International Edition, 62(29).
  Wolff, Benedikt; Qu, Zheng‐Wang; Grimme, Stefan & Oestreich, Martin
  
• Divergent Synthesis of 3-(Indol-2-yl)quinoxalin-2-ones and 4-(Benzimidazol-2-yl)-3-methyl(aryl)cinnolines via Polyphosphoric Acid (PPA)-Mediated Intramolecular Rearrangements of 3-(Methyl/aryl(2-phenylhydrazono)methyl)quinoxalin-2-ones. The Journal of Organic Chemistry, 88(24), 16864-16890.
  Mamedov, Vakhid A.; Mustakimova, Liliya V.; Qu, Zheng-Wang; Zhu, Hui; Syakaev, Victor V.; Galimullina, Venera R.; Shamsutdinova, Leisan R.; Rizvanov, Il’dar Kh.; Gubaidullin, Aidar T.; Sinyashin, Oleg G. & Grimme, Stefan
  
• Electron-deficient cyclopropenium cations as Lewis acids in FLP chemistry. Chemical Communications, 59(70), 10508-10511.
  Mandal, Dipendu; Qu, Zheng-Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Mechanism of Borane‐Catalyzed Oligomerization of Arylallenes and Arylacetylenes. European Journal of Organic Chemistry, 27(4).
  Qu, Zheng‐Wang; Zhu, Hui & Grimme, Stefan
  
• Organo-Group 2 Metal-Mediated Nucleophilic Alkylation of Benzene: Crucial Role of Strong Cation−π Interaction. ACS Catalysis, 13(3), 1686-1692.
  Qu, Zheng-Wang; Zhu, Hui; Streubel, Rainer & Grimme, Stefan
  
• Phosphino‐Phosphination Reactions: Frustrated Lewis Pair Reactivity of Phosphino‐Phosphonium Cations with Alkynes. Angewandte Chemie International Edition, 62(43).
  Kim, Hyehwang; Qu, Zheng‐wang; Grimme, Stefan; Al‐Zuhaika, Nahil & Stephan, Douglas W.
  
• Photoredox Catalyzed Single C−F Bond Activation of Trifluoromethyl Ketones: A Solvent Controlled Divergent Access of gem‐Difluoromethylene Containing Scaffolds. Chemistry – A European Journal, 29(12).
  Ghosh, Soumen; Qu, Zheng‐Wang; Roy, Sourav; Grimme, Stefan & Chatterjee, Indranil
  
• PI and PIII Ions Supported by BZIMPY Ligands. Chemistry – A European Journal, 29(70).
  LaFortune, James H. W.; Swidan, Ala'aeddeen; Ovens, Jeffrey S.; Qu, Zheng‐Wang; Grimme, Stefan; Land, Michael A. & Macdonald, Charles L. B.
  
• Reactivity of frustrated Lewis pairs with BOC protected diazocarboxylates: FLP capture of diazene. Chemical Communications, 59(41), 6191-6194.
  Hussain, Zahid; Luo, Yong-An; Wu, Yile; Qu, Zheng-Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Addition and NN bond cleavage of diazo-compounds by phosphino-phosphenium cations. Chemical Communications, 60(8), 1031-1034.
  Kim, Hyehwang; Lough, Alan; Qu, Zheng-wang; Grimme, Stefan & Stephan, Douglas W.
  
• Fluorination/Dearomatization of C6F5 Groups: An FLP Route to an Electrophilic Borane and Non‐Coordinating Anions. Chemistry – A European Journal, 30(43).
  Kim, Hyehwang; Mandal, Dipendu; Ng, Joshua Kye Jin; Qu, Zheng‐Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Mechanism of Alkaline Earth Metal Amide Catalyzed Hydrogenation of Challenging Alkenes and Arenes. ChemSusChem, 17(22).
  Qu, Zheng‐Wang; Zhu, Hui & Grimme, Stefan
  
• Reactivity of Frustrated Lewis Pair: Carbocation versus Radical Intermediates. Chemistry – A European Journal, 30(11).
  Qu, Zheng‐Wang; Zhu, Hui & Grimme, Stefan
  
• Readily accessible chiral frustrated Lewis pair catalysts: Asymmetric hydrosilylation of imines and quinolines. Chem Catalysis, 4(4), 100959.
  Guo, Jing; Jin, Lvnan; Xiao, Lei; Yan, Maying; Xiong, Jiangkun; Qu, Zheng-Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Silylium-Ion-Promoted (3 + 2) Annulation of Allenylsilanes with Internal Alkynes Involving a Pentadienyl-to-Allyl Cation Electrocyclization. Journal of the American Chemical Society, 146(46), 31377-31383.
  Zuo, Honghua; Qu, Zheng-Wang; Kemper, Sebastian; Klare, Hendrik F. T.; Grimme, Stefan & Oestreich, Martin
  
• Stereoconvergent Approach to the Enantioselective Construction of α‐Quaternary Alcohols by Radical Epoxide Allylation. Angewandte Chemie International Edition, 63(29).
  Höthker, Sebastian; Plato, Annika; Grimme, Stefan; Qu, Zheng‐Wang & Gansäuer, Andreas
  
• The impact of Lewis acid variation on reactions with di-tert-butyl diazo diesters. Dalton Transactions, 53(2), 439-443.
  Bedi, Vaibhav; Mandal, Dipendu; Hussain, Zahid; Chen, Shi-Ming; Wu, Yile; Qu, Zheng-Wang; Grimme, Stefan & Stephan, Douglas W.
  
• Photolytic and Thermal Reactions of [C6H4(PPh2)2(μ-N2)] and Its Lewis Acid Adducts: N–N Bond Cleavage and Liberation of N2. Journal of the American Chemical Society, 147(6), 4720-4725.
  Miao, Linkun; Yeung, Jason; Yeganeh-Salman, Amir; Qu, Zheng-wang; Grimme, Stefan & Stephan, Douglas W.