Ruthenium Cyclopentadienyl Aryldiazenido Complexes. Synthesis of [Cp‘Ru(PR3)2(N2C6H4OMe)][BF4]2and [Cp‘RuCl(PPh3)(N2C6H4OMe)][BF4] (Cp‘ = Cp, Cp*) and X-ray Crystal Structure of [CpRu(PPh3)2(N2C6H4OMe)][BF4]2, an Aryldiazenido Complex with a Large N−N−C(aryl) Angle and Near-Linear Ru−N−N−C(aryl) Skeleton

Abstract

The neutral ruthenium complexes Cp‘Ru(PR3)2Cl [Cp‘ = Cp, PR3 = PPh3, PMe3, or 1/2 dppe; Cp‘ = Cp*, PR3 = PMe3] react with [p-MeOC6H4N2][BF4] in acetone to give new cyclopentadienyl ruthenium aryldiazenido dicationic complexes [Cp‘Ru(PR3)2(N2C6H4OMe)][BF4]2 [Cp‘ = Cp, PR3 = PPh3 (1), PMe3 (2), or 1/2 dppe (3); Cp‘ = Cp*, PR3 = PMe3 (4)] in good yields. The dicationic complexes 1−3 may also be conveniently isolated in better yield by treatment of the acetonitrile ruthenium complexes [CpRu(PR3)2(NCMe)][BF4] with the arenediazonium salt. When the reaction of Cp‘Ru(PPh3)2Cl (Cp‘ = Cp or Cp*) with [p-MeOC6H4N2][BF4] is carried out in toluene, the product is instead the cyclopentadienyl ruthenium aryldiazenido monocationic complex [Cp‘RuCl(PPh3)(N2C6H4OMe)][BF4] [Cp‘ = Cp (5) or Cp* (6)]. Further, if the reaction of Cp*Ru(PPh3)2Cl with diazonium salt is carried out in acetone, the binuclear complex [Cp*RuCl(N2C6H4OMe)]2[Cl]2 (7) can be isolated in low yield in addition to 6. All new complexes 1−7 were fully char...