A Strained S<b>∼</b>C<b>∼</b>S Ir Pincer Complex: Intramolecular C−H Activation of an Aromatic Ring

Reaction of the bis(diphenylphosphino sulfide)methanide anion (S∼C∼S)− with [Ir(cyclooctene)2Cl]2 dimer complex affords an 18-VE Ir(III) hydrido complex. DFT calculations suggest that formation of this hydrido species results from the insertion of the highly reactive 16-VE Ir(I) complex [Ir(SCS)(cyclooctene)] into one of the C−H bonds of the phenyl group of a pendant phosphino sulfide ligand. The DFT results also point to the easy access to unsaturated intermediates, explaining the experimentally observed facile displacement of the cyclooctene ligand by PPh3.