Journal of the Chemical Society, Dalton Transactions p. 4039 - 4044 (1995)
Update date:2022-08-17
Topics:
Dyson, Paul J.
Humphrey, David G.
McGrady, John E.
Mingos, D. Michael P.
Wilson, D. James
The relative abilities of <2.2>paracyclophane (C16H16) and p-xylene (C6H4Me2-1,4) to form arene tricarbonyl complexes from chromium hexacarbonyl has been studied in dioxane using the Strohmeier reflux method, and the rate constants contrasted.The reactions are found to proceed more quickly with <2.2>paracyclophane by ca. 25percent.Density functional molecular-orbital calculations have rationalised this observation, and indicate that the enhanced reactivity of the <2.2>paracyclophane system relative to p-xylene is a consequence of repulsive interactions between the two arene decks in the former, which are relieved to some extent by co-ordination of the electron-withdrawing Cr(CO)3 fragment.
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