Reactions of (η5-C5Me5)Ir(PMe3)(SH)2 and (η5-C5Me5)Ir(PMe3)(SH)(H) with Thionylaniline (PhNSO) to Give Novel Iridium S3O and S2O Complexes

Treatment of Cp*Ir(PMe3)(SH)2 (1), where Cp* = η5-C5Me5, with thionylaniline (PhNSO), CS2, and p-tolylisothiocyanate (p-tolNCS) gave Cp*Ir(PMe3)(S3O) (3), Cp*Ir(PMe3)(S2CS) (4), and Cp*Ir(PMe3)(SH)(SC(S)HN-p-tol) (5), respectively. Treatment of Cp*Ir(PMe2R)(H)(SH) (2a,b), where R = Me (2a), Ph (2b), with PhNSO gave Cp*Ir(PMe2R)(S2O) (6a,b) as mixtures of interconvertible conformational isomers. Treatment of 2a with p-tolNCS gave Cp*Ir(PMe3)(H)(SC(S)NH-p-tol) (7). The crystal structures of 3−5, 6b, and 7 are reported.