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|Title:||Trends in the reactivity of the C pMn(CO) 2(η 2-arene) bond [arene = benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene]: an experimental and theoretical investigation|
|Citation:||Bengali, A.A., Fan, W.Y., Abdulrazak, K.T. (2009-06-08). Trends in the reactivity of the C pMn(CO) 2(η 2-arene) bond [arene = benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene]: an experimental and theoretical investigation. Organometallics 28 (11) : 3123-3128. ScholarBank@NUS Repository. https://doi.org/10.1021/om801185t|
|Abstract:||The displacement of η 2-coordinated arenes [arenes = benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene] from the photolytically generated C pMn(CO) 2(η 2-arene) complex by pyridine was studied. The substitution reaction proceeds by a dissociative mechanism, and the relative rates of displacement provide information about the interplay between electronic and steric factors in determining the overall stability of the Mn-(η 2-arene) bond. The regioselectivity of metal binding to the arene ligand was determined by examining the observed trends in the relative displacement rates for the xylenes. Theoretical modeling of the Mn-(η 2-arene) complexes lends support for the experimental analysis. Interestingly, unlike the other arenes, DFT (density functional theory) calculations suggest that mesitylene is bound to the Mn center by an arene C-H bond rather than by a C=C edge of the aromatic system. © 2009 American Chemical Society.|
|Appears in Collections:||Staff Publications|
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