Reactions between Carbonylhydridotris(triphenylphosphine)iridium(I) and Difluorophosphine Oxide, Sulphide, and Selenide: Identification of Ionic Intermediates

Article abstract of DOI:10.1039/DT9840002569

Carbonylhydridotris(triphenylphosphine)iridium(I) (1) reacts with PF2HY (Y= O, S, or Se) at 190 K in CH2Cl2 to give (2), identified by n.m.r. spectroscopy.When the solutions were allowed to warm above 220 K, PPh3 was liberated and complexes were formed .Complexes (3a) and (3b) were initially produced in two isomeric forms, with the PPh3 groups mutually cis or mutually trans; the cis isomer slowly isomerised to the trans isomer at room temperature.For complex (3c) (Y= O) only the trans isomer was detected.The complex was formed as a by-product in these reactions, and its n.m.r. parameters are reported.The implications of the formation of ionic intermediates in the reactions of (1) are briefly considered in relation to mechanisms of related reactions that are usually considered to involve initial loss of PPh3 from (1).

Full text of DOI:10.1039/DT9840002569

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