Abstract
Detailed kinetics studies of arene displacement by 1-hexene from the ten (arene)Cr(CO) 5 complexes (arene=C 6H 6− n (CH 3) n ; n=2−5) generated by pulsed laser flash photolysis have been conducted. The data indicate that all reactions obey a reversible dissociation-competition for the [Cr(CO) 5] intermediate mechanism. The systematic variations in rate constants for unimolecular dissociation of arenes in the presence of 1-hexene ‘trap’ strongly support ‘edge-on’ bonding of the arene to Cr for the methyl-substituted benzene compounds in which there is a CC ‘ring-edge’ unsubstituted by methyls. Where no such ring-edge is present, i.e., for mesitylene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene and pentamethylbenze, the kinetics data suggest that a rapid equilibrium is e stablished two binding modes, the second possibly through the ring center.
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