Organometallic Intermediates 

Introduction

Two techniques are used to investigate the structure and behaviour of unstable fragments and intermediates in organometallic reactions (particularly those relevant to homogeneous catalysis).
  1. Matrix isolation is a technique in which highly reactive species are generated by UV photolysis of stable precursors and trapped in inert solids. Recently, we have developed a method of using polyethylene (PE) as a matrix material for studying reactions in the presence of high pressures of gases (e.g. N2, H2 etc). Recent chemical examples include the synthesis of Cr(CO)4(H2)2 from Cr(CO)6+H2 and its subsequent reaction with N2. Currently we are using the technique to study catalytic reactions, e.g. hydrogenation, detecting the reactive intermediates by IR and the organic products by GC-MS.

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  2. Time-resolved IR allows us to identify intermediates in room temperature solution and to follow their reactions; examples include photochemistry of dinuclear metal compounds, intermediates in the photochemistry of CpRe(CO)3 and in organic photochemistry. Most recently, we have been using TRIR to understand how reactions in supercritical fluid solution differ from those in conventional organic solvents. Current research involves widespread overseas collaboration, including laboratories in Germany, Ireland, Japan, Russia and USA.

Further Information

For further information please contact M. W. George.

Key Publications

  1. Can Organometalic Noble Gas Compounds be observed in Fluid Solution at Room Temperature? A Time-resolved Infrared (TRIR) and UV Spectroscopic Study of the Photochemistry of M(CO)6 (M = Cr, Mo and W) in Supercritical Noble Gas and CO2 Solution, X-Z. Sun, M. W. George, S. G. Kazarian S. M. Nikiforov and M. Poliakoff, J. Am. Chem. Soc, 1996, 118, 10525-10532

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  2. Photochemistry of Cr(CO)4 (bpy) (bpy = 2,2’-Bipyridine) Studied by Time- Resolved Infrared Spectroscopy, I. G. Virrels, M. W. George, J. J. Turner, J. Peters, and A. Vlcek, Orgaonometallics, 1996, 15, 4089-4092.

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  3. UV Photochemistry of [CpFe(CO)2]2 followed by Picosecond Time-resolved Infrared Spectroscopy, M. W. George, T. P. Dougherty and E. J. Heilweil, J. Phys. Chem., 1996, 100, 201-206.

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  4. Photochemistry of [CpMo(CO)3]2 Direct Detection and Kinetics of the Radical CpMo(CO)3 in n-heptane Solution at Room Temperature by Fast Time-resolved Infrared Spectroscopy, J. Peters, M. W. George and J. J. Turner, Organometallics, 1995, 14, 1503-1506.

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  5. Unstable Species, CpW(CO)3 and [CpW(CO)3]2 studied by Fast Time- resolved Infrared Spectroscopy, I. Virrels, M. W. George, F. P. A. Johnson, J. J. Turner and J. R. Westwell, Organometallics, 1995, 14, 5203-5208.

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Created: July 1997
Last Revised: January 2001