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The synthesis and reactivity of electrophilic iridium (III) complexes containing bis (diphenylphosphino) ethane |
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| Authors: | Brian P Cleary and Richard Eisenberg |
| Institution: | Department of Chemistry, University of Rochester, Rochester, NY 14627, USA |
| Abstract: | The complex Ir(CH3) (CO) (CF3SO3)2 (dppe) (1) has been synthesized from the reaction of Ir(CH3)I2(CO) (dppe) and silver triflate. Methane and IrH(CO) (CF3SO3)2 (dppe) (2) are formed when a methylene chloride solution of 1 is placed under 760 torr dihydrogen. Conductivity studies indicate that methylene chloride solutions of complexes 1 and 2 are weak electrolytes and only partially ionized at concentrations above 1 mM. Complex 2 is an effective hydrogenation catalyst for ethylene and 1-hexene while acetone hydrogenation is inhibited by the formation of IrH2(HOCH(CH3)2) (CO) (dppe)] (OTf) (3). Linear dimerization and polymerization of styrene occurs via a carbocationic mechanism initiated by triflic acid elimination from 2. Treatment of an acetonitrile solution of Ir(CH3)I2(CO) (dppe) with silver hexafluorophosphate produces the solvent promoted carbonyl insertion product Ir(C(O)CH3) (NCCH3)3 (dppe)] PF6]2 (7) which readily undergoes deinsertion in methylene chloride to form Ir(CH3) (CO) (NCCH3)2 (dppe)] PF6]2 (8) and acetonitrile. |
| Keywords: | Catalysis Hydrogenation Polymerization Iridium complexes Carbonyl complexes Hydride complexes Alkyl complexes |
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