Synthesis and isomerisation of two metallated N,O-complexes of ruthenium: Models for the Murai reaction |
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| Authors: | Rodolphe FR Jazzar Andrew D Burrows Stuart A Macgregor Mary F Mahon |
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| Institution: | a Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
b School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK |
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| Abstract: | Two isomers of the N,O-coordinated acetylpyrrolyl complex Ru(PPh3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH‡ = 195 ± 41 kJ mol−1; ΔS‡ = 232 ± 62 J mol−1 K−1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions. |
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| Keywords: | Ruthenium complexes Phosphine ligands Hydride ligands Cyclometallation Murai reaction Density functional theory |
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