Catalysis and Catalytic Mechanisms

Homogeneous catalysis has emerged as one of the most powerful ways of functionalising organic molecules, both on a laboratory and a bulk scale. Our research has provided direct and indirect insight into catalysis in many ways:

  • development of the σ-Complex Assisted Metathesis mechanism, or σ-CAM, showing how the existence of complexes with σ-bonds coordinated to a transition metal can facilitate metathesis (with Sabo-Etienne, Toulouse)1
  • Scheme of sigma-Complex Assisted Metathesis mechanism
  • rates of oxidative addition of H–H, Si–H, C–H and B–H bonds2
  • detection of intermediates implicated in catalysis by laser flash, by matrix methods and by laser photolysis within an NMR probe
  • development of new catalytic borylation reactions (with Todd Marder, Durham)3
  • Study of B–H and B–B oxidative addition processes implicated in borylation4
  • synthesis of relatively stable species implicated in hydrosilation such as (C5H5)Rh(C2H4)(SiR3)H; study of their catalytic activity and of their stereochemical rearrangements5

Scheme showing mechanism of hydrosilylation complexes

  • study of the mechanism of catalytic transfer hydrogenation (with NPIL Pharma, Huddersfield)
  • Development of catalytic C–F bond activation at a polyfluorinated substrate5

Catalytic C-F Bond Activation

Selected Publications

  1. The σ-CAM mechanism: σ-complexes as the basis for σ-bond metathesis at late transition metal centers, Angew Chem Int Ed, 2007, 46, 2578-2592
  2. Photochemical oxidative addition of B-H bonds at ruthenium and rhodium, Chem Commun, 2004, 242-243.
  3. Ir-catalyzed borylation of C-H bonds in N-containing heterocycles, Angew Chem Int Ed, 2006, 45, 489-491
  4. Comparisons of photo-induced oxidative addition of B–H, B–B and Si–H bonds at rhodium(η5-cyclopentadienyl)phosphine centers, Organometallics 2006, 25, 5093-5104
  5. Photochemical reactions of (η5-cyclopentadienyl)bis(t-butylacrylate)rhodium with silanes, Dalton Trans, 2004, 3331.
  6. Catalytic C-F activation of polyfluorinated pyridines by nickel-mediated cross-coupling reactions, Chem Commun, 2001, 2254.