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Keywords:

  • Phosphane ligand, tripodal;
  • Iridium complex;
  • C[BOND]H activation, intramolecular

Abstract

The introduction of three methyl groups into the ipso positions of the cyclohexane ring in cis,cis-1,3,5-tris[diphenylphosphanyl)methyl]cyclohexane (tdppmcy) (1) leads to the new tripodal phosphane ligand cis,cis-1,3,5-tris(diphenylphosphanyl)methyl]1-1,3,5-trimethylcyclohexane (tdppmtmcy) (5). The dynamic behavior is studied by variable-temperature NMR spectroscopy and compared with the structure (X-ray analysis) in the solid state. Treatment of 5 with Ir(PPh3)2(CO)Cl gives 6 where the two PPh3 groups are replaced by two (diphenylphosphanyl)methyl groups of the ligand 5. In addition, an intramolecular C[BOND]H metalation takes place resulting in the oxidative addition of a ring methylene C[BOND]H bond to the metal. The X-ray structure of 6 is determined.