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1Author    Dieter Sellmann, Christine Rohm, Matthias Moll, Herrn Professor, H. P. FritzRequires cookie*
 Title    Protonierung und Alkylierung der  
 Abstract    Thiolatdonoren von Ru(II)-Komplexen mit [Ru(,buS5')]-Fragmenten ('buS5,-H 2 = 2,2'-Bis(2-mercapto-3,5-di-/-butylphenylthio)diethylsulfid) Transition Metal Complexes with Sulfur Ligands, CXV+. Protonation and Alkylation of Thiolate Donors in Ru(II) Complexes with [Ru('buS5')] Fragments ('buS5'-H 2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide) Reaction of meso-[Ru(L)(,buS5')] complexes (L = CO (1), PPh3, PCy3) with one equivalent of oxonium salts R3OBF4 (R = CH3, C2H5) yields the C, symmetrical monoalkyl derivatives [Ru(L)('buS5'-R)]BF4 (L = CO, R = CH3 (2), C2H5 (3); L = PPh3, R = CH3 (5); L = PCy3, R = CH3 (6)), in which one of the thiolate donors of the starting complexes is alkylated diastereospecifi-cally. Monoalkylation of the binuclear complex [Ru('buS5')]2 leads to Q symmetrical [Ru('buS5'-CH3)]2(BF4)2 (7) which gives the hydrazine complex [/i-N2H4{Ru('buS5'-CH3)}2](BF4)2-N2H4 (9) upon reaction with N2H4. Reaction of 1 with 1.5 equivalents of CF3S 03H yields the isolable thiol complex [Ru(CO)('buS5'-H)]CF3SOy0.5 CF3S03H (4). The 'H-NMR spectra are temperature-depen­ dent and indicate exchange of the thiol proton between the thiolate donors of the ,bus 5'2-ligand. Twofold protonation of 1 could only be proved IR-spectroscopically, dialkylation of 1, however, yields isolable [Ru(CO)('buS5'-(CH3)2)](BF4)2 (8) as a mixture of diastereomers. The IR stretching frequencies i/(CO) of the CO complexes indicate that the electron densities at the ruthenium centers are decreased and the Ru-L bonds are weakened. However, the ligands L in the [Ru(L)('buS5'-R)]BF4 complexes do not exchange more readily than in the parent complexes. Ubergangsmetallkomplexe mit Schwefelliganden, CXV+. 
  Reference    Z. Naturforsch. 50b, 1729—1738 (1995); eingegangen am 2. Mai 1995 
  Published    1995 
  Keywords    Ruthenium Sulfur Complexes, Alkylation, Protonation 
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 TEI-XML for    default:Reihe_B/50/ZNB-1995-50b-1729.pdf 
 Identifier    ZNB-1995-50b-1729 
 Volume    50