Complexes of ruthenium(II) and ruthenium(III) with tertiary arsines

Ruthenium trichloride reacts with stoichiometric amounts of tertiary arsines in boiling ethanol to give paramagnetic complexes, RuCl3(Ph2RAs)3 (R = Me, Et, Pr, Bu), which react further with 2,2′-bipyridyl(bipy) and o-phenanthroline(phen) to yield brick red crystalline products, RuCl3 (N-N)(Ph2RAs) (N-N = bipy, phen). In the presence of excess arsine Ru(III) is reduced to Ru(II), and trichloro-bridged complexes of the formula [Ru2Cl3(Ph2RAs)6]Cl are formed. These on treatment with carbonylated solutions of rhodium chloride produce yellow crystals of [Ru2Cl3(Ph2RAs)6][RhCl2(CO)2] containing Ru(II) and Rh(I). Several dicarbonyl complexes cis-RuX2(CO)2(Ph2RAs)2 (X = Cl, Br; R = Pr, Bu) have also been isolated. © 1977