An Unexpected Pathway for Ligand Substitution in an Aryl Halide Complex of Palladium

Authors

  • Zohrab Ahmadi,

    1. Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, BC V8W 3V6 (Canada), Fax: (+1) (250)-721-7147
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  • Prof. Allen G. Oliver,

    1. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (USA), Fax: (+1) (250)-721-7147
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  • Assoc. Prof. J. Scott McIndoe

    Corresponding author
    1. Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, BC V8W 3V6 (Canada), Fax: (+1) (250)-721-7147
    • Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, BC V8W 3V6 (Canada), Fax: (+1) (250)-721-7147
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Abstract

original image

A supposed spectator ligand plays a crucial role in a seemingly simple ligand substitution reaction on palladium. Continuous monitoring by ESI-MS reveals all the details of an initial fast displacement of iodide by an incoming phosphine ligand, and of the recoordination of iodide that prompts the displacement of the bidentate ligand actually being substituted. An apparent double substitution and subsequent isomerization can be readily explained by two fast and one slow ligand substitution reactions (see figure).

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