Question

The pressure dependence of the replacement of chlorobenzene (PhCl) by piperidine in the complex [W(CO)4(PPh)] has...

The pressure dependence of the replacement of chlorobenzene (PhCl) by piperidine in the complex [W(CO)4(PPh)] has been studied. The volume of activation is found to be + 11.3 cm 3 mol-1

What does this value suggest about the mechanism?

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Answer #1

The pressure depedence of replacement of chlorobenzene by piperidine in the complex [W(CO)4(PPh)] gave a volume of activation of +11.2 cm^3.mol-1.

The +ve value for the volume of activaion suggests the reaction has a cyclic transition state during the displacement of the chlorobenzene by piperdine. Also the +ve value in pressure dependence suggests that the reaction is deaccelerated by pressure. If a -ve value would had been obtained that would have had suggested acceleration of reaction by pressure.

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