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• W2334846522 startingPage "684" @default.
• W2334846522 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 characterized by NMR, FT-IR, and mass spectroscopies. The structure of [CpRu(PPh3)2(N2C6H4OMe)][BF4]2·0.93CHCl3 (1·0.93CHCl3) was determined by single-crystal X-ray diffraction. The structure exhibits a near-linear Ru−N−N−C geometry for the coordinated aryldiazenido group, with the NNC angle having a value of 159°, compared to the “sp2” value of approximately 120° commonly exhibited by other “singly bent” aryldiazenido complexes. On the basis of NMR spectroscopic data, 1 reacts with NaBH4 at low temperature to give an arylhydrazido(2−) complex [CpRu(PPh3)2{NN(H)C6H4OMe}][BF4], which readily converts to the corresponding aryldiazene complex [CpRu(PPh3)2(NHNC6H4OMe)][BF4] by a hydrogen shift; at room temperature, the only product is the hydrido complex CpRuH(PPh3)2." @default.
• W2334846522 created "2016-06-24" @default.
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• W2334846522 date "2000-01-21" @default.
• W2334846522 modified "2023-09-27" @default.
• W2334846522 title "Ruthenium Cyclopentadienyl Aryldiazenido Complexes. Synthesis of [Cp‘Ru(PR₃)₂(N₂C₆H₄OMe)][BF₄]₂ and [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−…" @default.
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• W2334846522 doi "https://doi.org/10.1021/om990761e" @default.
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