Cationic PCP iridaepoxide and carbene complexes for facile water elimination and activation processesElectronic supplementary information (ESI) available: Description of general methods, Fig. S1-S24 and crystallographic data for 2-NTf2, 4-Cl and 6-acetone. CCDC 1530796 and 1530797. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7dt00563f

Iridaepoxide dihydride complexes of a PCP ligand bearing benzo[ b ]thiophene linkers are synthesized through ligand coopertive N 2 O and H 2 activations. These neutral complexes also eliminate water at elevated temperatures to form the corresponding PC carbene P complexes which results in the formal hydrogenation of N 2 O to water. The synthesis of cationic iridaepoxide dihydride complexes are reported herein where the room temperature elimination of water is observed when a donating solvent is used. This supports a previously proposed mechanism for this water elimination where hydrides cis to the epoxide are required. Ir( i ) and Ir( iii ) cationic PC carbene P complexes are also synthesized through protonation and through O-H oxidation additions of water and phenol. Pathways for water activation and elimination at cationic iridium PCP pincer compounds are explored.