ABSTRACT An asymmetric t Bu POCN Triaz type pincer ligand containing a triazole arm was developed and used to generate iridium pincer complexes with different oxygen atom binding ancillary ligands. The structure and reactivity of the complexes [( t Bu POCN Triaz )Ir(H)(O 2 CCH 3 )], [( t Bu POCN Triaz )Ir(H)(acac)], and [( t Bu POC)Ir(H)(O 2 CCF 3 )] and its cationic derivatives were studied. The complexes could be successfully employed in the catalytic transfer dehydrogenation of alkanes as well as of unsaturated heterocycles.