A new family of heteroleptic bis-cyclometalated IrIII
complexes with formula [Ir(C
_
N)2(N
_
N)]Cl (C
_
N=2-phenylpyridinate
and N
_
N=2,2’-dipyridylamine or N-benzylated 2,2’-dipyridylamines,
were synthesized, characterized, and successfully
used as photosensitizers in the catalytic photooxidation of
an array of dialkyl, dibenzyl, alkyl aryl, and diaryl sulfides, as
well as sulfur-containing amino acids. Furthermore, the reactions
proceeded with optimal chemoselectivity, and atom
economy under mild conditions. Experimental observations
support a dual mechanism in which singlet oxygen and superoxide
are the actual oxidants.
