Synthesis, structure and reactivity of cationic rhodium(I) and iridium(I) thioether crowns: structures of [M([9]aneS3)(cod)]+(M = Rh, Ir; cod = cycloocta-1,5-diene) and [Rh([9]aneS3)(C2H4)2]+([9]aneS3= 1,4,7-trithiacyclononane)

Abstract

Reaction of M^I species with [9]aneS₃ affords half-sandwich complexes including [M([9]aneS₃)(cod)]⁺, [M([9]aneS₃)(coe)₂]⁺(M = Rh, Ir; coe = cyclooctene), [(Rh([9]aneS₃)(C₂H₄)₂]⁺, [Rh([9]aneS₃)(C₂H₄)(PR₃)]⁺(R = Ph, cyclohexyl), [Rh([9]aneS₃)(CO)(PPh₃)]⁺ and [Rh([9]aneS₃)(tcne)(NCMe)]⁺; crystal structure determinations of [M([9]aneS₃)(cod)]⁺(M = Rh, Ir) and [Rh([9]aneS₃)(C₂H₄)₂]⁺ confirm these complexes to be five-coordinate, and the latter species reacts with C–X (X = halide) bonds.