Catalysis with Main Group Substrates

The development of catalytic reactions has revolutionised the synthesis of organic molecules and polymers. In contrast, catalysis is virtually unexplored as a route to molecular and macromolecular inorganic materials. Over the past decade our group has been at the forefront of the development of catalytic reactions with main group substrates. In particular, we have been involved in a broad expansion of this field in the area of dehydrogenation and dehydrocoupling processes that allow access to a wide range of catenated structures based on elements across the p-block. Such catalytic pathways using main group substrates represent an increasingly attractive and convenient alternative to traditional routes such as salt metathesis and reductive coupling reactions. Applications of this work involve the fields of hydrogen storage and transfer, functional inorganic polymers, and ceramic thin films.

Selected Publications:

  1. Catalysis in Service of Main Group Chemistry: a Versatile Approach to p-Block Molecules and Materials.
    Leitao, E.M.; Jurca, T.; Manners, I.
    Nat. Chem., 2013, 5, 857.
  2. Non-Metal-Catalyzed Heterodehydrocoupling of Phosphines and Hydrosilanes: Mechanistic Studies of B(C6F5)3-Mediated Formation of P-Si Bonds
    Wu, L.; Chitnis, S. S.; Jiao, H.; Annibale, V. T.; Manners, I.
    J. Am. Chem. Soc., 2017, 139, 16780.
  3. Addition of a Cyclophosphine to Nitriles: An Inorganic “Click” Reaction Featuring Protio-, Organo-, and Main Group Catalysis
    Chitnis, S. S.; Sparkes, H. A.; Annibale, V. T.; Pridmore, N. E.; Oliver, A. M.; Manners, I.
    Angew. Chem. Int. Ed., 2017, 56, 9536.
  4. Homo- and Heterodehydrocoupling of Phosphines Mediated by Alkali Metal Catalysts
    Wu. L.; Annibale, V.; Jiao, H.; Brookfield, A.; Collison, D.; Manners, I.
    Nat. Commun., 2019, 10, 2786.
  5. Metal-Free Dehydropolymerisation of Phosphine-Boranes using Cyclic (Alkyl)(Amino)Carbenes as Hydrogen Acceptors
    Oldroyd, N.L.; Chitnis, S.S.; Annibale, V.T.; Arz, M.A.; Sparkes, H.A.; Manners, I.
    Nat. Commun., 2019, 10, 1370.
  6. Trivalent Titanocene Alkyls and Hydrides as Well-Defined, Highly Active, and Broad Scope Precatalysts for Dehydropolymerization of Amine-Boranes
    LaPierre, E.A.; Patrick, B.O.; Manners, I.
    J. Am. Chem. Soc., 2019, 141, 20009.
  7. Ring-Opening Polymerization of Cyclic Phosphonates: Access to Inorganic Polymers with a Pv-O Main Chain
    Arz, M.A.; Annibale, V.T.; Kelly, N.L.; Hanna, J.V.; Manners, I.
    J. Am. Chem. Soc., 2019, 141, 2894.
  8. Polyphosphinoborane Block Copolymer Synthesis Using Catalytic Reversible Chain-Transfer Dehydropolymerization
    Race, J.J.; Heyam, A.; Wiebe, M.A.; Hernandez, J.D.G.; Ellis, C.E.; Lei, S.; Manners, I.; Weller, A.S.
    Angewandte Chemie, 2023, 62, e202216106.
  9. Transition-Metal-Free Dehydropolymerization of Phosphine–Boranes at Ambient Temperature
    Wiebe, M.A.; Kundu, S.; LaPierre, E.A.; Patrick, B.O.; Manners, I.
    Chem. Eur. J., 2023, 29, e202202897.
  10. A Crystalline Monomeric Phosphaborene
    LaPierre, E.A.; Patrick, B.O.; Manners, I.
    J. Am. Chem. Soc., 2023, 145, 7107.
  11. Synthesis of a Carbene-Stabilized (Diphospha)aminyl Radical and Its One Electron Oxidation and Reduction to Nonclassical Nitrenium and Amide Species
    LaPierre, E.A.; Wantanabe, L.; Patrick, B.O.; Rawson, J.M.; Tuononen, H.M.; Manners, I.
    J. Am. Chem. Soc., 2023, 145, 9223.