| Abstract: | Here, we report an iridium(III) coordination system with 2‐aminoethanethiolate (aet), which shows the formation of S?H???S hydrogen and S?S disulfide bonds in a controlled manner. Treatment of fac‐Ir(aet)3] with aqueous HBF4 under aerobic conditions gave dinuclear Ir2(aet)4(cysta)]2+ ( 1 ]2+; cysta=cystamine) with a single S?S disulfide bond, while dimeric Ir2(aet)3(Haet)3](BF4)3 ( 2 ](BF4)3) with a triple S?H???S hydrogen bond was formed by similar treatment under anaerobic conditions. Upon exposure to air, 2 ]3+ was converted to dinuclear Ir2(aet)2(Haet)2(cysta)]4+ ( 3 ]4+), in which two IrIII centers are spanned by a double S?H???S hydrogen bond and a single S?S disulfide bond. Complex 3 ]4+ was interconvertible with 1 ]2+ via the removal/addition of protons on S donors, accompanied by the intermolecular exchange of the fac‐Ir(aet)3] units. Complexes 1 ]2+, 2 ]3+, and 3 ]4+, isolated as BF4? salts, were fully characterized by single‐crystal X‐ray crystallography. |
