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


• 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

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

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.