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1997 (1)
1983 (1)
1Author    Z. NaturforschRequires cookie*
 Title    Synthesis of Cationic Ruthenium Thioketene Complexes through Intramolecular 1,2-Elimination [1]  
 Abstract    Halfsandwich thiocarboxylate complexes [CpRu(PR3)->(SC(0)CH2R')] ((P R 3)2 = (PPh3)2, Ph2PCH 2PPh2 (dppm), Ph2PC2H4PPh2 (dppe); R' = C6H 5, 4-C6H4Me, 4-C6H 4OMe, 4-C6H4C1) are obtained from the corresponding thiolate complexes [CpRu(PR3)2SH] and acyl chlorides. The structure of [CpRu(dppm)(SC(0)CHTPh)] was determined: monoclinic space group P2j/c (No. 14), a = 9.229(2), b = 16.680(3),"c = 21.447(5)Ä, ß = 90.751(12)°, Z = 4. Reaction of the thiocarboxylate complexes with the anhydrides of either trifluoro-acetic acid or trifluoromethanesulfonic acid gives thioketene complexes [CpRu(dppm) (?;2-S=C=CHR')]PF(s. H ie structure of [CpRu(dppm)0/2-S= C = C H Ph)]PF6 was deter­ mined: monoclinic space group P2,/c (No. 14), a -13.814(5), b -15.338(2), c = 17.057(7) Ä, ß = 93.74(2)°, Z = 4. 
  Reference    (Z. Naturforsch. 52b, 117—124 [1997]; received July 25 1996) 
  Published    1997 
  Keywords    Ruthenium Complexes, Thiocarboxylate, Thioketene, Structure 
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 TEI-XML for    default:Reihe_B/52/ZNB-1997-52b-0117.pdf 
 Identifier    ZNB-1997-52b-0117 
 Volume    52 
2Author    M. Torres, A. Clement, 0. P. StrauszRequires cookie*
 Title    Argon-Matrix Isolation of Bis(carbomethoxy)thiirene: Formation of Acyl and Carbalkoxythioketenes  
 Abstract    Photolysis of argon-matrix isolated 4,5-bis(carbomethoxy)-l,2,3-thiadiazole with A = 254 or 265 nm resulted in the almost quantitative formation of bis(carbomethoxy)-thiirene (3g). Photolysis of 3g could only be carried out by long irradiation times at short wavelength A = 210nm and resulted mainly in extensive fragmentation instead of the formation of bis(carbomethoxy)thioketene, confirming earlier predictions that substituents, especially electron-withdrawing ones, should stabilize the thiirene ring. Methylcarboethoxy and methylacetylthioketene were obtained, however, in the argon-matrix photolysis or flow thermolysis of 4-methyl-5-carboethoxy-or 4-carboethoxy-5-methyl-l,2,3-thiadiazole and 4-acetyl-5-methyl-l,2,3-thiadiazole, respectively. 
  Reference    Z. Naturforsch. 38b, 1208—1212 (1983); received June 6 1983 
  Published    1983 
  Keywords    Thiirene, Thioketene, 1, 2, 3-Thiadiazole, Thio-Wolff Rearrangement 
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 TEI-XML for    default:Reihe_B/38/ZNB-1983-38b-1208.pdf 
 Identifier    ZNB-1983-38b-1208 
 Volume    38