Mechanism of oxidative addition of allylic halides to iridium(I) complexes

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Abstract

A detailed study has been made of the oxidative addition reaction of allylic halides to IrCI(CO)(P(CH3)2C6(H5)2 in benzene in methanol. In benzene the reaction probably occurs by way of a π-allyl intermediate. This reacts with anion to give a product with α ò-ally group bonded to the metal cis to the added anion. Both crotyl α-methylallyl chlorides give the same products since they form the same π-allyl. In methanol the π-allyl is not an intermediate since crotyl chloride α-methylallyl chloride give different σ-allyl products with the metal atom bonding predominantly to the carbon atom bearing the chloride. The anion which add in methanol can be one added to the solution it bonds trans to the σ-allyl group. A modified SN2 mechanism with double-bond participation is proposed for both solvents.

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    1

    Present address Chemistry Department University of California Santa Barbara, CA 93106.

    2

    Present address chemistry Department Rutgers University Newark New Jersey 07102.

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