Organoindium compounds of redox active 1,2‐benzenedithiolate and 2‐amidobenzenethiolate ligands were synthesized and tested for reactivity against mild oxidants. The reaction of Me3In and (NCN)InMe2 [NCN=2,6‐bis(dimethylaminomethy)phenyl] with 3,4‐toluenedithiol (H2tdt) at room temperature afforded [MeIn(tdt)(py)]2 (1) and (NCN)In(tdt) (2), respectively. A similar reaction of Me3In with 2‐aminobenzenethiol (H2abt) in toluene under reflux afforded [MeIn(abt)(py)]2 (3). The reaction of (NCN)InCl2 with one equivalent of Li2(abt) or two equivalents of Li(Habt) afforded the compounds [(NCN)In(abt)]⋅LiCl(thf)2 (4⋅LiCl(thf)2) and (NCN)In(Habt)2 (5), respectively. The X‐ray crystal structures of 1 and 3 are similar and show dimeric structures via μ‐S‐(tdt) and μ‐N‐(abt) ligands, respectively. Compounds 2 and 4 possess similar monomeric structures and tridentate NCN pincer ligands. DFT computational studies have been used to rationalize the observed solid‐state structures and discern the potential reactivity of compounds 1–4 against oxidants. The reaction of 1 and 2 with excess iodine resulted in loss of the 3,4‐toluenedithiolate ligand and the formation of the oligomeric disulfide [tdt]n, while 3 and 4 showed no reactivity under similar conditions. This contrasts the reactivity of previously reported organoindium o‐amidophenolate complexes which undergo oxidative addition of iodine to afford ligand‐centered radical species. [ABSTRACT FROM AUTHOR]

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