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.