34692-10-9Relevant academic research and scientific papers
Reactions of 'GaI' with organometallic transition metal halides
Coombs, Natalie D.,Stasch, Andreas,Aldridge, Simon
, p. 449 - 456 (2008)
Two approaches towards the synthesis of phosphine ligated half-sandwich complexes [(ηx-CxHx)M(PR3)2GaI2]n containing diiodogallyl ligands have been investigated. Insertion of 'GaI' into the Mo-I bond of (η7-C7H7)Mo(CO)2I has been shown to yield the crystallographically characterized dimeric complex [(η7-C7H7)Mo(CO)2GaI2]2 (2). Attempts to substitute the carbonyl ligands by the phosphine ligand dppe [dppe = bis(diphenylphosphino)ethane] have been shown instead to yield the sparingly soluble complex [(η7-C7H7)Mo(CO)2GaI2]2(μ-dppe) (3) in which the phosphine bridges two [(η7-C7H7)Mo(CO)2GaI2] units via a pair of P → Ga donor/acceptor bonds. By contrast, attempts to insert 'GaI' directly into the metal-halogen bond of phosphine ligated complexes such as (η5-C5H5)Ru(PPh3)2Cl or (η5-C5H5)Ru(dppe)Cl have been shown to result in the formation of the tetraiodogallate species(η5-C5H5)Ru(PPh3)2(μ-I)GaI3 (5) and [(η5-C5H5)Ru(dppe)]+[GaI4]- (7).
Halogen exchange by reaction of CpRu(Cl)(PPh3)2 with MeC(O)X (X = Br, I) and its mechanistic study
Kuniyasu, Hitoshi,Sanagawa, Atsushi,Nakajima, Takuya,Iwasaki, Takanori,Kambe, Nobuaki,Bobuatong, Karan,Ehara, Masahiro
supporting information, p. 34 - 37 (2014/08/18)
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.
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
Hirano, Masafumi,Murakami, Masahiro,Kuga, Toshinori,Komine, Nobuyuki,Komiya, Sanshiro
, p. 381 - 393 (2012/05/07)
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
Reactions of furylruthenium complexes with oxygen and trimethylsilyl azide
Chang, Ku-Hsien,Sung, Hui-Ling,Lin, Ying-Chih
, p. 649 - 655 (2007/10/03)
The reaction of the (α-alkoxyfuryl)ruthenium complexes 4 with oxygen opens the five-membered furyl ring to give the addition product [Ru]O 2CCR=CHCO2CH3, (5, [Ru] = Cp(PPh 3)2Ru). Further reactions of
Reactions of ruthenium cyclopropenyl complexes with trimethylsilyl azide
Chang,Lin,Liu,Wang
, p. 3154 - 3159 (2007/10/03)
Treatment of the phenyl substituted cyclopropenyl complex [Ru]-C=C(Ph)CHPh (1a, [Ru]= (η5-C5H5)(PPh3) 2Ru) with Me3SiN3 in THF in the presence of NH4PF6 at
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
Fan, Li,Einstein, Frederick W. B.,Sutton, Derek
, p. 684 - 694 (2008/10/08)
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.
Binding and activation of halocarbons by iron(II) and ruthenium(II)
Kulawiec, Robert J.,Faller,Crabtree, Robert H.
, p. 745 - 755 (2008/10/08)
A series of cyclopentadienylruthenium(II) and -iron(II) complexes contain intact iodoalkanes, p-iodotoluene, or chelating (P, X) (o-halophenyl)diphenylphosphine (X = Cl, Br) ligands. The halocarbons coordinate via σ-donation of a halogen lone pair and ret
Interconversion of persulfido, sulfur hydride, and hydride ligands coordinated to CpRu(PPh3)2+
Amarasekera, Jayantha,Rauchfuss, Thomas B.
, p. 3875 - 3883 (2008/10/08)
The electron-rich metallothiol CpRu(PPh3)2SH (1) has been prepared from the reactions of CpRu(PPh3)2Cl with NaSH and CpRu(PPh3)2H with elemental sulfur. Carbonylation of 1 gives CpRu(PPh3)(CO)SH whereas the carbonylation of CpRu(PPh3)2Cl is thermodynamically unfavorable. Protonation of 1 gives [CpRu(PPh3)2(SH2)]+. Alkylation of 1 gives thiol complexes [CpRu(PPh3)2(RSH)]+ (R = CH3); such complexes were also prepared directly from CpRu(PPh3)2OTf (OTf = CF3SO3) and RSH. The structure of the thiol complex [CpRu(PPh3)2(n-PrSH)]BF4·CH 2Cl2 was determined by X-ray methods. Crystal data: triclinic space group P1, with a = 13.308 (5) A?, b = 14.641 (7) A?, c = 13.205 A?, α = 113.64 (3)°, β = 110.01 (4)°, γ = 84.45 (3)°, V = 2212 (2) A?3, and Z = 2; structure solution and refinement based on 4091 reflections with I > 2.58σ(I) to give R = 0.054. [CpRu(PPh3)2(SH2)]+ reacts reversibly with H2 to give the dihydride [CpRu(PPh3)2H2]+. Analogous results were found for [((2-SC4H3)CH2C5H 4)Ru(PPh3)2]+; the S-bound thiophene ligand can be displaced by H2S, H2, H-, and SH-. [CpRu(PPh3)2(H2S)]+ oxidizes in air to give [CpRu(PPh3)2]2(μ-S2)2+ (2). Salts of 2 are formed in two-electron oxidations of 1 with Ph3CBF4, Cp2Fe+, and I2 as well as electrochemically. A presumed intermediate in this oxidation is [CpRu(PPh3)2]2(μ-S2)+. This mixed-valence compound disproportionates upon addition of HOTf to give 2 and [CpRu(PPh3)2(SH2)]+. The reaction of 1 with sulfur gave ruthenium polysulfides [CpRu(PPh3)]2Sx (x = 4, 6).
Oxidative cleavage reactions of compounds of the type CpRuLL′R (L, L′ = CO, PPh3; R = Me, PhCH2)
Joseph, Michael F.,Page, John A.,Baird, Michael C.
, p. 1749 - 1754 (2008/10/08)
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
