New ruthenium(III) and ruthenium(II) complexes containing triphenyl-arsine and -phosphine and other ligands

Abstract

A detailed investigation of the reactions of [RuX₃(Eph₃)₂MeOH](A)(X = Cl or Br; E = P or As) with ligands containing nitrogen (alkyl and aryl cyanides, pyridine, 2,2′-bipyridyl, 1,10-phenanthroline), sulphur (dimethyl sulphoxide, dialkyl sulphides, carbon disulphide, sodium diphenylphosphinodithioate), oxygen (tetrahydrofuran, acetone, nitromethane) and carbon (norbornadiene, 1,5-cyclo-octadiene, carbon monoxide) donor atoms is presented. Five different types of behaviour towards these ligands are exhibited by (A): (1) displacement of methanol giving the ruthenium(III) compounds [RuX₃(Eph₃)₂L], e.g. L = RCN, Me₂SO, CS₂, CS; (2) displacement of methanol and one Eph₃ group giving [RuX₃(Eph₃)L₂], e.g. L₂= Me₂S, bipy, C₅H₅N; (3) complete displacement of methanol. Eph₃ and X without reduction, e.g.[Ru(S₂PPh₂)₃]; (4) reduction to ruthenium(II) with or without complete displacement of Eph₃ groups, e.g.[RuX₂L₂(Eph₃)₂](L₂= CO, C₇H₈,RCN) and [RuX₂L₄](L = C₅H₅N, Me₂SO); (5) reduction to cationic ruthenium(II) compounds in methanol, e.g.[RuCl(PPh₃)(N–N)₂]Cl [(N–N)= bipy or phen]. Several of these compounds can also be synthesised from [RuX₂(PPh₃)₃]. The compounds are characterised by elemental analyses, molecular weights, e.s.r., and magnetic measurements, and configurations tentatively suggested on the basis of detailed far-i.r. [ruthenium(III)] and ¹H n.m.r. [ruthenium(II)] studies. Finally, electronic spectra (50 000–12 000 cm^–1) are presented and discussed.