Director of Research

+44 (0)131 451 8031
Room 2.16
William Perkin Building
Heriot-Watt University
Stuart Macgregor
Roles and responsibilities
  • Director of Research, School of Engineering and Physical Sciences

Computational Organometallic Chemistry

Research uses computational chemistry to model reaction mechanisms in transition metal organometallic chemistry. Methods employed include density functional theory, hybrid QM/MM calculations and molecular dynamics. We aim to understand challenging bond activation processes (C-H and C-F bond cleavage), rationalise unusual reactivity patterns and model multi-step catalytic cycles. Research is usually carried out in close collaboration with experimental chemists.

1. Ambiphilic Metal-Ligand Assisted (AMLA) C-H Activation

We have developed the concept of Ambiphilic Metal-Ligand Assisted (AMLA) C-H activation. In this process an agostic interaction to an unsaturated metal centre combines with H-bonding to a basic co-ligand to facilitate C-H bond cleavage. With aromatic C-H activation at [Pd(OAc)2] this mechanism supersedes the long-proposed Wheland-type intermediate.  AMLA can account for facile C-H bond cleavage of both e--deficient and e--rich aromatic substrates at a range of late transition metal centres.

Figure 1. Computed agostic Intermediate in the AMLA-6 C-H Activation of dimethylbenzylamine at [Pd(OAc)2].

2. Metallophosphoranes and Aromatic C-F Bond Activation

We have defined novel ligand-assisted mechanisms for breaking the strong C-F bond of fluoroaromatics. This process involves nucleophilic attack by an e--rich metal centre with addition of a C-F bond over the M-L moiety, where L can be PR3, SiR3 or BR2. For L= PR3 metallophosphoranes, [LnM-(PFR3)], are formed as intermediates or transition states. Metallophosphoranes also play a role in the unusual M-F/P-R exchange reactions, such as the interconversion of [RhF(PPh3)3] to [Rh(Ph)(PFPh2)(PPh3)2].


Figure 2. The central role of metallophosphoranes in phosphine-assisted C-F bond activation and F/R exchange processes.

3. Ruthenium N-Heterocyclic Carbene (NHC) Complexes in Catalysis

NHC ligands often confer enhanced reactivity on metal complexes. An example is the hydrodefluorination of C6F5H to give 1,2-C6F4H2 catalysed by [Ru(H)2(CO)(NHC)(PR3)2] species. Calculations show this unusual ortho-selectivity arises from a nucleophilic attack mechanism where the hydride ligand (and not the metal) acts as the reacting species. Calculations also aim to understand the stability of NHC ligands towards metal-based decomposition reactions such as C-H, C-C and C-N activation.


Figure 3. Nucleophilic attack of a hydride ligand at the ortho position of C6F5H.

Selected publications
  1. 'Synthesis and Characterization of a Rhodium(I) σ-Alkane Complex in the Solid State', S. D. Pike, A. L. Thompson, A. G. Algarra, D. C. Apperley, S. A. Macgregor and A. S. Weller, Science, 2012, 337, 1648.
  2. 'Competing C-F Activation Pathways in the Reaction of Pt(0) with Fluoropyridines: Phosphine-Assistance versus Oxidative Addition', A. Nova, S. Erhardt, N. A. Jasim, R. N. Perutz, S. A. Macgregor, J. E. McGrady and A. C. Whitwood, J. Am. Chem. Soc., 2008, 130, 15499.
  3. 'Mechanisms of catalyst poisoning in palladium-catalyzed cyanation of haloarenes. Remarkably facile C-N bond activation in the [(Ph3P)4Pd]/[Bu4N]+ CN- system', S. Erhardt, V. V. Grushin, A. H. Kilpatrick, S. A. Macgregor, W. J. Marshall and D. C. Roe, J. Am. Chem. Soc., 2008, 130, 4828.
  4. 'Activation of an Alkyl C-H Bond Geminal to an Agostic Interaction: An Unusual Mode of Base-Induced C-H Activation', L. J. L. Häller, M. Page, S. A. Macgregor, M. F. Mahon and M. K. Whittlesey, J. Am. Chem. Soc., 2009, 131, 4604.
  5. 'Mechanisms of C-H bond activation: rich synergy between computation and experiment', Y. Boutadla, D. L. Davies, S. A. Macgregor and A. I. Poblador-Bahamonde, Dalton Trans., 2009, 5820.
Further information

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