Pentamethylcyclopentadienyl-rhodium and -iridium complexes. Part 17. Complexes with sulphur-containing ligands

Abstract

Preparations and properties of the following η⁵-pentamethylcyclopentadienyl-rhodium and -iridium complexes are reported: [{Rh(C₅Me₅)}₂Cl₄(SMe₂)], [Rh(C₅Me₅)(SMe₂)₃][PF₆]₂, [Rh(C₅Me₅)(MeCN)(dithian)][PF₆]₂, [{Rh-(C₅Me₅)}₂(SS)Cl₄](SS = 1,4-dithian, 2,5-dithiahexane), [Rh(C₅Me₅)(2,5-dithiahexane)₂][PF₆]₂[Rh(C₅Me₅)-Cl(SR)]_n(R = Me, Ph, and PhCH₂), [Rh(C₅Me₅)Cl(S₂CNEt₂)], [Rh(C₅Me₅)(S₂CNMe₂)₂], [Rh(C₅Me₅)-(S₂CMe)₂], [Rh(C₅Me₅){S₂C₂(CN)₂}], [{Rh(C₅Me₅)(3,4-S₂C₆H₃Me)}₂], [Ir(C₅Me₅)(S₂CNMe₂)₂], and [Ir-(C₅Me₅){S₂C₂(CN)₂}]. The complexes [Rh(C₅Me₅)(S₂CNMe₂)₂], [Rh(C₅Me₅)(S₂CMe)₂], and [Ir(C₅Me₅)-(S₂CNMe₂)₂] have one uni- and one bi-dentate dithio-ligand.

A range of Rh^I and Pd^II 1,4-dithian (dt) complexes have also been prepared including [{RhCl(dt)_n}]-[{PdX₂(dt)}_n](X = Cl or Br), [{RhL₂(dt)}_n][PF₆][n= 2, L = PPh₃, P(OPh)₃; n= 1, L₂= cyclo-octa-l,5-diene or norbornadiene] and [Pd(L)(dt)][PF₆](L =η³2-methylallyl and η³-1-phenylallyl). The poisoning of the [{Rh(C₅Me₅)Cl₂}₂]-catalysed olefin hydrogenation by S-containing ligands is contrasted with the ability of some of the above sulphur complexes to catalyse olefin hydrogenation under certain conditions.