- Halogen exchange by reaction of CpRu(Cl)(PPh3)2 with MeC(O)X (X = Br, I) and its mechanistic study
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The treatment of CpRu(Cl)(PPh3)2 with MeC(O)X offers a very convenient procedure for the synthesis of CpRu(X)(PPh3) 2. The proposed mechanism involves an intermediate produced by the concerted liberation of PPh3 by the incoming MeC(O)X and the subsequent subtraction of the X atom by the Ru atom to form a radical pair.
- Kuniyasu, Hitoshi,Sanagawa, Atsushi,Nakajima, Takuya,Iwasaki, Takanori,Kambe, Nobuaki,Bobuatong, Karan,Ehara, Masahiro
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- Ruthenium cyclopentadienyl aryldiazenido complexes. Synthesis of [Cp′Ru(PR3)2(N2C6H 4OMe)][BF4]2 and [Cp′RuCl(PPh3)(N2C6H 4OMe)][BF4] (Cp′ = Cp, Cp*) and x-ray crystal structure of [CpRu(PPh3)2
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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(N2C6H 4OMe)]-[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)(N2C6H 4OMe)][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(N2C6H 4OMe)][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}][BF 4], which readily converts to the corresponding aryldiazene complex [CpRu(PPh3)2(NH=NC6H4OMe)][BF 4] by a hydrogen shift; at room temperature, the only product is the hydrido complex CpRuH(PPh3)2.
- Fan, Li,Einstein, Frederick W. B.,Sutton, Derek
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- Acid-promoted sp3 C-H bond cleavage in a series of (2-allylphenoxo) ruthenium(II) complexes. Mechanistic insight into the aryloxo-acid interaction and bond cleavage reaction
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A series of RuCp[OC6H3(CH2CH=CH 2-2)(R)](PPh3)n complexes (n = 2, R = H (1a); n = 1, R = 4-OMe (2b), 4-Me (2c), 4-Ph (2d), 4-Br (2e), 4-NO2 (2f), 6-OMe (2g), 6-Me (2h), 6-Ph (2i)) have been
- Hirano, Masafumi,Murakami, Masahiro,Kuga, Toshinori,Komine, Nobuyuki,Komiya, Sanshiro
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p. 381 - 393
(2012/05/07)
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- Heterobimetallic complexes with dppm-bridged Ru/Pd, Ru/Pt, Ru/Au and Ru/Cu centers
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The heterobimetallic Ru/Pd, Ru/Pt, Ru/Au and Ru/Cu complexes Cp(PPh3)Ru(μ-I)(μ-dppm)PdCl2 (4), Cp(PPh3)Ru(μ-Cl)(μ-dppm)Pd(CH3)Cl (5), Cp(PPh3)Ru(μ-I)(μ-dppm)PtCl2 (6), Cp(PPh3)Ru
- Yang, Ying,Abboud, Khalil A.,McElwee-White, Lisa
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p. 4288 - 4296
(2007/10/03)
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- Reactions of Transition Metal o-Acetylide Complexes. XIII. Alkylation and Related Reactions
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A series of 20 cationic vinylidene complexes of ruthenium and osmium + (R = Me, Ph, C6H4F-4, C6F5, (CH2)2C2H; R' = Me, CH2Ph, CH2CH=CH2, CH2CCH, (CH2)3Br; L, L' = PPh3, CNBut, dppm, dppe; not all combinations)., 2>2+ and 2>2+ have been obtained from reactions between the metal acetylide complexes and the appropriate organic halides.
- Bruce, Michael I.,Humphrey, Mark G.
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p. 1067 - 1076
(2007/10/02)
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- A VERSATILE ROUTE TO (η5-C5R5)RuL2X FROM ALLYLMETHYLRUTHENIUM COMPLEXES
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Divalent ruthenium complexes, (η5-C5R5)RuL2X (R=H, CH3; X=Br, Cl), are formed by thermal decomposition of (η5-C5R5)Ru(CH3)X(η3-C3H5) in the presence of several neutral ligands.
- Nagashima, Hideo,Yamaguchi, Keitaro,Mukai, Katsunori,Itoh, Kenji
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p. C20 - C22
(2007/10/02)
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- Oxidative cleavage reactions of compounds of the type CpRuLL′R (L, L′ = CO, PPh3; R = Me, PhCH2)
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The compounds CpRuLL′R (Cp = η5-C5H5; L, L′ = CO, PPh3; R = Me, PhCH2) have been prepared, some by improved routes. Alkyl cleavage reactions with halogens, hydrogen chloride, mercury(II) halides, and
- Joseph, Michael F.,Page, John A.,Baird, Michael C.
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p. 1749 - 1754
(2008/10/08)
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- CYCLOPENTADIENYL-RUTHENIUM COMPLEXES. 1 THE REACTIVITY OF SOME ?-CYCLOPENTADIENYL-BISTRIPHENYLPHOSPHINE-RUTHENIUM(II) COMPLEXES
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Several ruthenium complexes of the CpRuX(PPh3)2 type, where X=Cl, Br, I, NCS, NCO, CN, BH4, H, D, and some of the CpRuS2CZ(PPh3) type, where Z=NR2 or OR, were obtained.The hydride CpRuH(PPh3)2 was obtained in high yield by reaction of CpRuCl(PPh3)2 with R
- Wilczewski, Tadeusz,Bochenska, Maria,Biernat, Jan F.
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