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'Protonation' in keywords Facet   section ZfN Section B  [X]
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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 
2Author    A. Heinrich, W. PreetzRequires cookie*
 Title    Darstellung und Schwingungsspektren von Alkyl-und Rhodanohydrohexaboraten Preparation and Vibrational Spectra of Alkyl and Rhodano Hydrohexaborates  
 Abstract    Treatment of B 6 H 6 2 " with iodoalkanes and (SCN) 2 in organic solvents affords the monosubsti-tuted protonated hexaborates RB 6 H 6 ", R = CH 3 , C 2 H 5 < C 3 H 7 , C 4 H 9 , C 8 H 17 and SCN, respective-ly. The acidity constants of these weak Brönsted acids range for the alkylated species from 8.8 to 9.6, and for R = SCN the pk a value is ~5. From basic solutions the salts Cs 2 RB 6 H 5 can be precipitated, which show band patterns in the IR and Raman spectra typical for monosubstituted hydrohexaborates. The protonated compounds RB 6 H 6 " are distinguished from the corresponding Brönsted bases RB 6 H 5 2 " by a high frequency shift of the BH stretching vibrations in the order of 100 cm" 1 . For Cs 2 (SCN)B 6 H 5 , S coordination of SCN" is supposed because of the high frequency of v CN : 2144 cm" 1 . 
  Reference    Z. Naturforsch. 43b, 1327—1331 (1988); eingegangen am 8. Juli 1988 
  Published    1988 
  Keywords    Alkylhydrohexaborates, Rhodanohydrohexaborate, Protonation, IR Spectra, Raman Spectra 
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 TEI-XML for    default:Reihe_B/43/ZNB-1988-43b-1327.pdf 
 Identifier    ZNB-1988-43b-1327 
 Volume    43 
3Author    DavidJ. Brauer, Jörg Fischer, Stefan Kucken, KlausP. Langhans, O. Thm, Ar Stelzer, Norbert WeferlingRequires cookie*
 Title    Wasserlösliche Phosphane, III [1] Wasserlösliche primäre Phosphane mit Ammoniumgruppierungen NR2R' in der Seitenkette -donorfunktionalisierte Amphiphile Water-Soluble Phosphanes, III [1] Water-Soluble Primary Phosphanes with Ammonium Groups NR2R' in the Side Chain -Donor-Functionalized Amphiphiles  
 Abstract    Primary and secondary aminoalkylphosphanes R2N -(C H 2)" ,-P H 2 (R 2 = Me2, «Bu2, C5H 10, C4H 80 , 2-(l-Methyl-2-pyrrolidinyl); m = 2, 3, 6, 10, 11; 1 -6) or [R2N -(C H 2)m]2PH (7, R2 = C5H 10; m = 2) are accessible by aminoalkylation of PH 3 with tö-chloroalkylamines R2N -(C H 2)m-C l in the superbasic medium DM SO/KOH (DM SO = dimethylsulfoxide). By selective N-quaternization of 1, 2, 4 -6 with RT (R ' = Me, C"H2" + 1; n = 6 -8 , 12, 16, 18) in the two-phase system CH2C12/H 20 novel primary phosphanes [R 'R 2N -(C H 2)m-P H 2]+I~ (ll-1 6 f) with quaternary ammonium groups in the alkyl side chain are obtained. The water solubility of l l -1 6 f decreases with increasing chain length (n) of R'. 11 (R = R' = Me; m = 2) shows a trans conformation at the C2H 4 bridge according to an X-ray structural analysis. Protonation of 1, 2, 4, 5 with HC1 affords the water-soluble hydrochlorides [HR2N -(C H 2)" ,-P H 2]+C1~ (19-22). The cationic primary phosphanes l l -1 6 f are stable towards oxygen. By oxidation of 11 with one or two equivalents of H 20 2 the primary phos­ phane oxide [Me3N -(C H 2)2-P (0) H 2]+I~ (23) or the phosphonous acid [Me3N -(C H 2)2-P (0)(0 H)H ]+I~ (23aj are formed. Hofmann degradation of 11 or 16c with KOH yields phosphirane in good yields. Reaction of 1, 2, 4 -6 (L) with Fe2(CO)9 at ambient temperature yields stable complexes (CO)4FeL (26-30). U nder more rigorous conditions Fe3 clusters (31, 32) with free R2N groups are obtained. 
  Reference    Z. Naturforsch. 49b, 1511—1524 (1994); eingegangen am 16. Mai 1994 
  Published    1994 
  Keywords    Aminoalkylphosphanes, Protonation, Water Solubility, Complexes, Clusters 
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 TEI-XML for    default:Reihe_B/49/ZNB-1994-49b-1511.pdf 
 Identifier    ZNB-1994-49b-1511 
 Volume    49 
4Author    H. Schumann, B. Neumann, H.-G StammlerRequires cookie*
 Title    Spektroskopische und strukturelle Aspekte der Protonierung von Tetraaza[14]annulen-Dianionen Spectroscopic and Structural Aspects of the Protonation of Tetraaza[14]annulene Dianions  
 Abstract    The effects of increasing protonation upon two [ 14]annulene dianions prepared by reaction of LiCH3 with 5,14-dihydro-6,8,15,17-tetram ethyldibenzo[b,i][l,4,8,l l]tetraazacyclotetradecine 
  Reference    Z. Naturforsch. 51b, 1255—1266 (1996); eingegangen am 8. Februar 1996 
  Published    1996 
  Keywords    Nickel Complexes, Macrocyclic Ligands, Protonation, 7r-Conjugation, X-Ray 
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 TEI-XML for    default:Reihe_B/51/ZNB-1996-51b-1255.pdf 
 Identifier    ZNB-1996-51b-1255 
 Volume    51