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 RhI and PdII 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.