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'Sulfur Ligands' in keywords Facet   Publication Year 2000  [X]
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1Author    WolfdieterA. Schenk, Nikolai KuhnertaRequires cookie*
 Title    Synthesis of Halfsandwich Ruthenium Complexes of Sulfinic Acid Esters [1]  
 Abstract    A series of halfsandwich ruthenium sulfinato complexes [CpRu(PR'3)2(SO:R)] (R = Me, CH 2Ph, C2H4Ph, Ph, 4 -CöH4Me; PR'3 = PM e3, 1/2 dppm) with various electronic and steric environments around the ruthenium centre, have been prepared by insertion of SO2 into a ruthenium carbon bond, by a direct ligand exchange reaction, or by oxidation of thiolato complexes with 3-chloroperoxybenzoic acid. The chiral complexes [CpRu(C0)(PPh3)(S0 2 R)] (R = Me, CH2Ph, Ph) were obtained similarly by oxidation of the corresponding thiolates with magnesium monoperoxyphthalate. Alkylation of the sulfinato complexes with oxonium salts [Rm 3 0 ]X (R" = Me, Et; X = B F 4 , PF6) gave ruthenium complexes of sulfinic acid esters, [C pRu(L)(L')(S(0)(0R ")R)]X in high yields and, for the chiral complexes, up to 82% de. The esters may be detached from the metal by ligand exchange with acetonitrile. Stronger nucleophiles such as I~ or SMe~ dealkylate the coordinated sulfinic acid esters. 
  Reference    Z. Naturforsch. 55b, 527—535 (2000); received March 20 2000 
  Published    2000 
  Keywords    Ruthenium Complexes, Sulfur Ligands, Diastereoselective Alkylations 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0527.pdf 
 Identifier    ZNB-2000-55b-0527 
 Volume    55 
2Author    Dieter Sellmann, Daniel Häußinger, Torsten Gottschalk-Gaudig, FrankW. HeinemannRequires cookie*
 Title    Übergangsmetallkomplexe Activated CH2 Groups, and Interionic Interactions in the Solid State ('pybuS4'2-= 2,6-Bis(2-mercapto-3,5-di-terf-butylphenylthio)dimethylpyridine(2-))  
 Abstract    mit Schwefelliganden, 145 [1]. [Ru(NO)(,py^M S4 ,)]Br, ein Komplex mit [Ru(NO)(NS4)]-Gerüst, aktivierten CH2-Gruppen und interionischen Wechselwirkungen im Festkörper ['p y ^ S ^ 2* = 2,6-Bis(2-mercapto-3,5-di-terM>utyl-phenylthio)dimethylpyridin(2-)] Transition Metal Complexes with Sulfur Ligands, 145 [1]. [Ru(NO)('pybuS4')]Br, a Complex with [Ru(NO)(NS4)] Core, In the search for soluble and reactive ruthenium nitrosyl complexes, [Ru(NO)('pybuS4')]Br ([2]Br) was synthesized by template alkylation of NBu4[Ru(NO)('buS2')2] with py(CH',Br)2 ['pybuS4'2-= 2,6-bis(2-mercapto-3,5-di-ter/-butyl-phenylthio)dimethylpyridine(2-); '°US2 = 2-mercapto-3,5-di-terf-butylphenylthiolate(2-); py(CH2Br)2 = 2,6-bis(bromomethyl)pyridine]. The solid state structure of 2 has been determined by X-ray diffraction, which reveals a head-to-head 0 -0 interaction between the linear Ru-NO entities. The ligand CH 2 protons of [2]+ are activated and exchange with D+ under ambient conditions. The /^(NO) band of [2]Br appears at 1841 cm -1 in the solid state (KBr or hostaflon mull) and is significantly blue-shifted in solution (1879 cm-1 in MeOH, 1886 cm -1 in DMF). A similar blue-shift (1866 cm -1 in KBr vs. 1888 cm -1 in MeOH) has been found for [Ru(NO)('pyS4')lBr ([l]B r) which contains the parent [Ru(NO)('pyS4')]+ cation ['pyS4'2-= 2,6-bis(2-mercaptophenylthio)dimethylpyr-idine(2-)]. These t^(NO) shifts can be explained either by an interionic charge-transfer between the bromide anions and the nitrosyl complex cation or by 0 -0 interactions between two NO ligands as found for solid-state [2]Br. These interactions are not found for [l]O Ts which exhibits a ^(N O) band at ca. 1890 cm -in the solid state (KBr, hostaflon) as well as in MeOH solution. 
  Reference    Z. Naturforsch. 55b, 723—729 (2000); eingegangen am 5. April 2000 
  Published    2000 
  Keywords    Ruthenium Nitrosyl Complexes, Sulfur Ligands, Interionic Interaction 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0723.pdf 
 Identifier    ZNB-2000-55b-0723 
 Volume    55