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(NHC)Ni(0)-Catalyzed Branched-Selective Alkene Hydrosilylation with Secondary and Tertiary Silanes

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(NHC)Ni(0)-Catalyzed Branched-Selective Alkene Hydrosilylation with Secondary and Tertiary Silanes
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  • Alison Sy-min Chang
    Alison Sy-min Chang
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
    More by Alison Sy-min Chang
  • Kiana E. Kawamura
    Kiana E. Kawamura
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
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  • Hayden S. Henness
    Hayden S. Henness
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
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  • Victor M. Salpino
    Victor M. Salpino
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
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  • Jack C. Greene
    Jack C. Greene
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
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  • Lev N. Zakharov
    Lev N. Zakharov
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
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  • Amanda K. Cook*
    Amanda K. Cook
    Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
    *Email: [email protected]
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    Orcidhttps://orcid.org/0000-0003-3501-8502
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ACS Catalysis

Cite this: ACS Catal. 2022, 12, 18, 11002–11014
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https://doi.org/10.1021/acscatal.2c03580
Published August 31, 2022
Copyright © 2022 American Chemical Society
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Abstract

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Hydrosilylation is a valuable approach for the construction of organosilanes, which are precursors to silicone materials that are widely incorporated in our everyday lives. The industry currently relies primarily on Karstedt’s catalyst, Pt2(dvtms)3 (dvtms = 1,3-divinyltetramethyldisiloxane), a precious metal catalyst that exhibits linear selectivity, with regioselectivity favoring the branched product remaining an outstanding challenge. The use of more Earth-abundant, base-metal catalysts has been a recent focus for hydrosilylation reactions, and most reports focus on the development of linear-selective catalysts and are commonly limited to primary and/or secondary silanes. We demonstrate that (NHC)Ni(0) (NHC = N-heterocyclic carbene) complexes are active in the branched-selective hydrosilylation of alkenes with secondary or tertiary silanes, including industrially relevant alkoxy- and chlorosilanes. The scope of alkenes and silanes has been expanded beyond what is currently known for Ni-catalyzed hydrosilylation reactions, including both steric and electronic profiles. In-depth mechanistic studies were also carried out, including stoichiometric and catalytic experiments investigating kinetic and thermodynamic reaction parameters. Radical trap experiments suggest against a one-electron pathway. The rate law of the reaction has a normal dependence on the Ni catalyst and silane and has an inverse dependence on the alkene. Deuterium-labeling studies reveal that hydrosilylation proceeds through a Chalk–Harrod-type mechanism, with the alkene reversibly inserting into a Ni–H bond. Hammett analyses show that the rate of reaction is faster with electron-rich alkenes and electron-poor silanes. Additional mechanistic evidence points to the resting state of the catalyst being a (NHC)Ni(alkene)2 complex, and the rate-determining step being migratory insertion and/or reductive elimination.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.2c03580.

  • Details on synthetic procedures; characterization of products; crystal structure of 1g; kinetics data; and NMR, IR, and HRMS characterization (PDF)

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This article is cited by 30 publications.

  1. Xianyang Long, Dong Zhu, Shifa Zhu. Cobalt-Catalyzed Chemoselective and Divergent Synthesis of Vinylsilanes through Hydrosilylation of Acetylene. ACS Catalysis 2025, 15 (6) , 4429-4440. https://doi.org/10.1021/acscatal.5c00006
  2. Jinyu Zhang, Jiawei Guo, Wanlin Liu, Min Liu, Dongbing Zhao. Nickel(0)-Catalyzed Stereospecific and Enantioselective Ring-Opening Hydrosilylation of Methylenecyclopropanes to Access (E)-Homoallylsilanes. ACS Catalysis 2025, 15 (4) , 3126-3133. https://doi.org/10.1021/acscatal.4c07799
  3. Alison Sy-min Chang, Melanie A. Kascoutas, Quinn P. Valentine, Kiera I. How, Rachel M. Thomas, Amanda K. Cook. Alkene Isomerization Using a Heterogeneous Nickel-Hydride Catalyst. Journal of the American Chemical Society 2024, 146 (22) , 15596-15608. https://doi.org/10.1021/jacs.4c04719
  4. Chunyu Chen, Xin Yi, Ke-Fang Yang, Ze Li, Guo-Qiao Lai, Pinglu Zhang. Palladium-Catalyzed Cross-Coupling Polymerization of Bis-N-tosylhydrazones and Bis(silyl) Aryls: A New Access to Polycarbosilane Synthesis. Macromolecules 2023, 56 (24) , 10192-10197. https://doi.org/10.1021/acs.macromol.3c02018
  5. Masahiro Kamitani, Kazuki Kanemitsu, Kouta Yujiri, Hidetaka Yuge. Iron Pivalate Complexes Containing PNN Pincer Ligand: Synthesis and Application to Dehydrogenative Hydrosilane Coupling. Organometallics 2023, 42 (14) , 1839-1848. https://doi.org/10.1021/acs.organomet.3c00161
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  8. Bartłomiej Szarłan, Jakub Robaszkiewicz, Piotr Pawluć, Maciej Kubicki, Maciej Zaranek. Salen-type nickel( ii ) complexes for distinct selective hydrosilylation of alkenes under mild conditions. Dalton Transactions 2025, 54 (17) , 7088-7094. https://doi.org/10.1039/D4DT03257H
  9. Nobuki Katayama, Kazuki Tabaru, Tatsuki Nagata, Miku Yamaguchi, Takeyuki Suzuki, Takashi Toyao, Yuan Jing, Zen Maeno, Ken-ichi Shimizu, Takeshi Watanabe, Yasushi Obora. Recyclable and air-stable colloidal manganese nanoparticles catalyzed hydrosilylation of alkenes with tertiary silane. RSC Advances 2025, 15 (3) , 1776-1781. https://doi.org/10.1039/D4RA08380F
  10. Shunqin Chang, Yueping Lin, Pei Gu, Changhui Lu, Minyan Wang, Liangbin Huang. Ligand -controlled nickel-catalyzed C–O bond cleavage of silyl enol ether for the divergent synthesis of aryl alkenes and silicon-containing product. Organic Chemistry Frontiers 2025, 54 https://doi.org/10.1039/D4QO01906G
  11. Dachang Bai, Kangbao Zhong, Lingna Chang, Yan Qiao, Fen Wu, Guiqing Xu, Junbiao Chang. Nickel-catalyzed regiodivergent hydrosilylation of α-(fluoroalkyl)styrenes without defluorination. Nature Communications 2024, 15 (1) https://doi.org/10.1038/s41467-024-50743-w
  12. Andrei A. Tereshchenko, Irina K. Goncharova, Alexander D. Zagrebaev, Sergei V. Chapek, Irina O. Nechitailova, Dmitrii Yu. Molodtsov, Alexander V. Soldatov, Irina P. Beletskaya, Ashot V. Arzumanyan, Alexander A. Guda. Heterophase Pt/EG-catalyzed hydrosilylation in droplet microfluidics: Spectral monitoring and efficient 3D-printed reactors. Chemical Engineering Journal 2024, 498 , 155016. https://doi.org/10.1016/j.cej.2024.155016
  13. Siobhan S. Wills, Corinne Bailly, Michael J. Chetcuti. Towards Nickel–NHC Fluoro Complexes—Synthesis of Imidazolium Fluorides and Their Reactions with Nickelocene. Molecules 2024, 29 (18) , 4493. https://doi.org/10.3390/molecules29184493
  14. Irina K. Goncharova, Irina P. Beletskaya, Ashot V. Arzumanyan. Prospects in Sustainable Hydrosilylation by Biphase Catalysis. ChemCatChem 2024, 16 (15) https://doi.org/10.1002/cctc.202400155
  15. Ryohei Doi, Sensuke Ogoshi. Chemical Strategies for the Cleavage of the C(sp 3 )−F Bonds in Perfluoroalkyl Groups. European Journal of Organic Chemistry 2024, 27 (11) https://doi.org/10.1002/ejoc.202301229
  16. T. Wiesner, M. Haas. Update Hydrometallation Group 4 (Si, Ge and Sn). 2024https://doi.org/10.1016/B978-0-323-96025-0.00125-3
  17. Irina K. Goncharova, Stepan A. Filatov, Anton P. Drozdov, Andrei A. Tereshchenko, Pavel A. Knyazev, Alexander A. Guda, Irina P. Beletskaya, Ashot V. Arzumanyan. White-Light initiated Mn2(CO)10/HFIP-Catalyzed anti-Markovnikov hydrosilylation of alkenes. Journal of Catalysis 2024, 429 , 115269. https://doi.org/10.1016/j.jcat.2023.115269
  18. Abdollah Neshat, Rahimeh Khezri, Mohammad Reza Yousefshahi, Mohammad Gholinejad, Fahimeh Varmaghani. Carbon−Sulfur Coupling Reactions Catalyzed by Nickel(II) N‐Heterocyclic Carbene Complexes. European Journal of Inorganic Chemistry 2023, 26 (36) https://doi.org/10.1002/ejic.202300437
  19. Suresh Saini, Dharmendra Kumar Gupta, Ramesh Bhawar, Sheema Siddiqui, Manoj V. Mane, Shubhankar Kumar Bose. Transition-metal- and solvent-free regioselective hydrosilylation of alkenes and allenes enabled by catalytic sodium tert -butoxide. Green Chemistry 2023, 25 (23) , 10072-10081. https://doi.org/10.1039/D3GC03473A
  20. Benon P. Maliszewski, Eleonora Casillo, Perrine Lambert, Fady Nahra, Catherine S. J. Cazin, Steven P. Nolan. Simply accessible platinum( ii ) complexes enabling alkene hydrosilylation at ppm catalyst loadings. Chemical Communications 2023, 59 (94) , 14017-14020. https://doi.org/10.1039/D3CC05033E
  21. Nobuki Katayama, Yasushi Obora. Recent developments in alkene hydrosilylation utilizing manganese catalysts. Tetrahedron Letters 2023, 132 , 154798. https://doi.org/10.1016/j.tetlet.2023.154798
  22. Benon P. Maliszewski, Tahani A. C. A. Bayrakdar, Perrine Lambert, Lama Hamdouna, Xavier Trivelli, Luigi Cavallo, Albert Poater, Marek Beliš, Olivier Lafon, Kristof Van Hecke, Dominic Ormerod, Catherine S. J. Cazin, Fady Nahra, Steven P. Nolan. Pt II −N‐Heterocyclic Carbene Complexes in Solvent‐Free Alkene Hydrosilylation. Chemistry – A European Journal 2023, 29 (40) https://doi.org/10.1002/chem.202301259
  23. Sanghyup Seo, Joonho Jung, Hyunwoo Kim. Palladium‐Catalyzed Hydrosilylation of Unactivated Alkenes and Conjugated Dienes with Tertiary Silanes Controlled by Hemilabile Hybrid P , O Ligand. Angewandte Chemie 2023, 135 (28) https://doi.org/10.1002/ange.202303853
  24. Sanghyup Seo, Joonho Jung, Hyunwoo Kim. Palladium‐Catalyzed Hydrosilylation of Unactivated Alkenes and Conjugated Dienes with Tertiary Silanes Controlled by Hemilabile Hybrid P , O Ligand. Angewandte Chemie International Edition 2023, 62 (28) https://doi.org/10.1002/anie.202303853
  25. Katsuaki Kobayashi, Norihisa Fukaya, Hiroshi Nakazawa. Catalytic hydrosilylation using an immobilized Co-terpyridine complex activated by inorganic salts and its application in a flow reactor. New Journal of Chemistry 2023, 47 (25) , 11784-11791. https://doi.org/10.1039/D3NJ01062G
  26. Boon Chong Lee, Chen-Fei Liu, Leroy Qi Hao Lin, Kang Zheng Yap, NingXi Song, Charyl Hui Min Ko, Priscilla Hee Chan, Ming Joo Koh. N-Heterocyclic carbenes as privileged ligands for nickel-catalysed alkene functionalisation. Chemical Society Reviews 2023, 52 (9) , 2946-2991. https://doi.org/10.1039/D2CS00972B
  27. Shigeru Shimada. Recent Advances of Group 10 Transition Metal Hydrosilylation Catalysts. 2023, 13-93. https://doi.org/10.1007/3418_2023_99
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  30. Katsuaki Kobayashi, Hiroshi Nakazawa. Research on inorganic activators of dibromo Co-terpyridine complex precatalyst for hydrosilylation. Dalton Transactions 2022, 51 (48) , 18685-18692. https://doi.org/10.1039/D2DT03471A
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ACS Catalysis

Cite this: ACS Catal. 2022, 12, 18, 11002–11014
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https://doi.org/10.1021/acscatal.2c03580
Published August 31, 2022
Copyright © 2022 American Chemical Society
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