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1995 (299)
61Author    Uwe Rosenthal, Siegmar Pulst, PerditaA. Rndt, Wolfgang Baumann, Annegret Tillack, R. Hett KempeRequires cookie*
 Title    Zum Ligandeinfluß in neuen Ni(0)-Komplexen disubstituierter Butadiine On the Influence of Ligands in New Ni(0) Complexes of D isubstituted Butadiynes  
 Abstract    It has been shown that disubstituted butadiynes react with L2Ni(C2H 4) to yield m ono­ nuclear complexes L2Ni(?/2(l:2)-R C = C -C = C R) (L = o-T ol-0)3P, R = SiMe3 (1), 'Bu (2), Ph (3)). For the first time, the crystal structure of a nickel(O) alkyne complex carrying phosphite ligands (2) has been determined. The reaction of (dipy)Ni(cod) (L2 = dipy) with butadiynes R 'C = C -C = C R is strongly influenced by the substituents of the butadiyne. With R' = R = SiMe3 (4), 'Bu (5) and Ph (6) or R' = Ph, R = SiMe3 (7) and R ' = 'Bu, R = SiMe3 (8) mononuclear complexes (dipy)Ni(?72(l:2)-R 'C = C -C = C R) have been observed. Depending on the stoichiometry with R = R ' = Ph (9) and 'Bu (10) dinuclear complexes |(dipy)Ni}2(/<-?72(l:2),?72(3 :4)-R 'C = C -C = C R) having two Ni atoms coordinated to two C = C triple bonds were obtained. By contrast, with R ' = R = SiMe3 (11), R' = 'Bu, R = SiMe3 (12) and R' = Ph, R = SiMe3 (13) the two Ni-centers were found to coordinate to the same C = C triple bond to yield another type of a dinuclear complex {(dipy)Ni}2(w-?72(l:2),//2(l:2)-R 'C = C -C = C R). Com pound 5 has been characterized by X-ray crystal structure analysis. The structures of 2 and 5 are com pared to that of the well-known complex (Ph3P)2Ni(?72(l:2)-'B u C = C -C = C 'B u) [1] to study the influence of different ligands L on the structural details. In comparison to the alkyne complexes L2Ni(//2-R C = C R) in butadiyne complexes of the L2Ni(//2(l:2)-R 'C = C -C = C R) type there is only a slight effect of the different ligands. The uncomplexed C = C triple bond as a part of the second substi­ tuent in conjugation to the complexed C = C triple bond appears to level out the influence of ligands and substituents. 
  Reference    Z. Naturforsch. 50b, 368—376 (1995); eingegangen am 4. O ktober 1994 
  Published    1995 
  Keywords    Butadiyne, Phosphite, Dipyridyl, Crystal Structure, Nickel(O) Complexes 
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 Identifier    ZNB-1995-50b-0368 
 Volume    50 
62Author    Requires cookie*
 Title      
 Abstract    2),?72 (3 :4) -P h C = C -C = C P h) [15]. 
  Reference    Z. Naturforsch. 50b, 377—2 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0377 
 Volume    50 
63Author    Requires cookie*
 Title    X . (i)  
 Abstract    can be considered as a R R 'C 2+ synthon. A n a p p a r­ ent extension to these findings will be the study on similar reactions with trithio ortho esters and tetrathio o rtho carb on ates which may serve as R C 3+ and C4+ synthons, respectively. In this paper, we repo rt the scope and lim itation of the nickel-catalyzed alkylative alkenation of trith io o rth o ­ esters and tetrath io orth o carb on ates [6]. MeMgX Me Me NiCl2 (dppe) (2) Results and Discussion A . Prototype cross coupling reactions o f benzylic trithioorthoesters The starting trithioorthoesters 1 were obtained from the reaction of the anion of dithianes with 
  Reference    Z. Naturforsch. 50b, 385 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0385 
 Volume    50 
64Author    Requires cookie*
 Title    PentamethylcycIopentadienylbis  
 Abstract    (ethen)eisen -ein 17e-Halbsandwichkomplex mit leicht verdrängbaren Ethenliganden P en tam ethylcyclopentadienylbis(ethene)iron -a 17 e H alfsandw ich C om plex w ith Easily D isplaceable E th en e Ligands K laus Jonas*, P eter K lusm ann, R ichard G o d d ard 
  Reference    Z. Naturforsch. 50b, 394 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0394 
 Volume    50 
65Author    W. Ilhelm, V. D. Ahlhoff, K. Arin, R. Adkow SkiRequires cookie*
 Title    Amphiphilic Carbohydrate-Based Mesogens, 10 [1] Synthesis of Mesogenic 2-O-w-Alkyl-L-threitols  
  Reference    Z. Naturforsch. 50b, 405 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0405 
 Volume    50 
66Author    Requires cookie*
 Title    Synthesis, Characterization and Monoalkene Polymerization Activity of Bis-[(l,2,3,4-tetraphenyl)-i75-cyclopentadienyl]zirconium(IV) Dichloride  
  Reference    Z. Naturforsch. 50b, 411 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0411 
 Volume    50 
67Author    Requires cookie*
 Title    Tetrabutylammonium Salts of 2-Nitropropane, Cyclopentadiene and 9-Ethylfluorene: Crystal Structures and Use in Anionic Polymerization  
  Reference    Z. Naturforsch. 50b, 415 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0415 
 Volume    50 
68Author    Requires cookie*
 Title    Ethen/l-Hexen-und 1-Octadecen-Copolymerisation mit dem stereorigiden Zirkon-Katalysatorsystem /Pr(CpFlu)ZrCl2/MAO: Einfluß der Temperatur  
  Reference    Z. Naturforsch. 50b, 423 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0423 
 Volume    50 
69Author    W. Ilhelm, Keim* H Eiko, M. Aas, StefanM. EckingRequires cookie*
 Title    Palladium Catalyzed Alternating Cooligomerization of Ethylene and Carbon Monoxide to Unsaturated Ketones  
 Abstract    C hem ie d er R W TH A achen, W orringer Weg 1, D-52074 A achen, G erm any D edicated to Prof. Dr. Dr. h.c. mult. Günther Wilke on the occasion o f his 70th birthday Z. N aturforsch. 50b, 4 3 0 -4 3 8 (1995); received S ep tem b er 15, 1994 C ooligom erization, C arbonylation. Palladium , H em ilabile, U n satu rated K etone C ationic palladium catalysts have been used to cooligom erize ethylene and carbon m onox­ ide. A t high eth y len e/C O ratios (m /m = 10:1) in m ethylene chloride as a solvent, u n satu rated alternating cooligom ers of the general stru ctu re R [C (0)C H 2C H 2],"H (m>l; R ^ C H 2=CH -, C H 7=CHCH'>CH2-and C H 3C H = C H C H 2-) w ere o b tain ed for the first time. Single com ponent catalyst precursors [(allyl)P d(P AX)]+Y~ (P AX = P h " P (C H 9) " C (= 0) 0 R , P h ,P (C H 2)2P (= 0)P h 2, Ph2/ 5(C H 2)"C = C H C H = C H 5 , Ph2P (C H 2)2S (= 0)P h , n = 1 -3 , R -Me, Et; Y~ = BF4_, SbF6') with b identate P.O-and P,S-ligands as well as in situ catalysts with unfunctionalized phos-phine ligands w ere used. W ith P "B u3 as a ligand, selectivities for ethylvinylketone of 40% based on the C O converted w ere obtain ed . The hem ilabile phosphino-ester and phosphino-thiophene ligands behave like m o n o d en tate phosphines un d er catalytic conditions. 
  Reference    Z. Naturforsch. 50b, 430 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0430 
 Volume    50 
70Author    Roland Köster3, Günter Seidel3, Roland Boeseb, Bernd WrackmeyercRequires cookie*
 Title    Ein tricyclisches Tetraboradisiladodecan aus Dimethyl-di-l-propinylsilan und Ethyldiboranen(6) [1] A Tricyclic Tetraboradisiladodecane from Dimethyl-di-l-propynylsilane and Ethyldiboranes(ö) [1]  
 Abstract    a M ax-Planck-Institut für K ohlen forsch un g, K aiser-W ilhelm -Platz 1, D -45466 M ülheim an der R uhr b Institut für A norganische C h em ie der U n iversität E ssen , U niversitätsstraße 5 -7 , D -4 5 117 E ssen c Laboratorium für A n organ isch e C h em ie der U n iversität Bayreuth, 
  Reference    Z. Naturforsch. 50b, 439 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0439 
 Volume    50 
71Author    JörgJ. Schneider, GoddardCarl Richard, KrügerRequires cookie*
 Title    Oxidative Abbaureaktionen des homonuklearen Cobalthydridclusters [<)/5-Cp*)Co]3H4 Oxidative Degradation Reactions of the Homonuclear Cobalt Hydride Cluster [(?75-Cp*)Co]3H4  
 Abstract    K ohlenforschung. K aiser-W ilhelm -Platz 1, 45470 M ülheim an der Ruhr Z. N aturforsch. 50b, 4 4 8 -4 5 9 (1995); ein gegan gen am 4. O ktober 1994 O xid ative D egrad ation, C luster D egrad ation, Cluster o f C p * -C o The h om on uclear cobalt cluster [(//5-C p *)C o]3H 4 2 reacts with various organic and inorganic substrates with co m p lete degradation o f the cluster core to afford m ainly m o n o n u ­ clear organom etallic cobalt com pounds. Thus, w hereas reaction o f the cluster with CO, N O or alkynes results in the retention o f the C o3 ring, the cluster reacts with Br2, I2, I2/C O , I2/ P (C 2H 5)3, CC14, H C I3, (C H 2)2Br2, H acac, C H 2Br2, (C 6H 5C O)O O C (C H 3)3, H B F 4, and BrC N to give m on on u clear com p lexes or bridged dinuclear com p lexes w ithout a m etal-m etal bond. In all cases form al oxid ation o f the m etal cen ter is observed. The crystal structures o f six organocobalt co m p lex es have been d eterm ined by X-ray crystallography. 
  Reference    Z. Naturforsch. 50b, 448 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0448 
 Volume    50 
72Author    Jens Heilmann, WilhelmF. MaierRequires cookie*
 Title    Problems in Selective Catalysis with Molecular Imprints in Silica -Selective Lactones Formation from Hydroxyesters in Micropores  
 Abstract    K ohlenforschung. K aiser-W ilhelm -Platz 1, D -45470 M ülheim an der Ruhr 
  Reference    Z. Naturforsch. 50b, 460 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0460 
 Volume    50 
73Author    Gerhard Erker, Christian Psiorz, Roland FröhlichRequires cookie*
 Title    A Rigid Cj-Bridged Ansa-Zirconocene-Derived Catalyst System Suited for Stereoselective Low Molecular Weight Polypropylene Formation  
 Abstract    O rgan isch -C hem isches Institut der U niversität M ünster, C orrensstraße 40, D -48149 M ünster 
  Reference    Z. Naturforsch. 50b, 469 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0469 
 Volume    50 
74Author    Beate Becker, Borislav Bogdanović+Requires cookie*
 Title    [TiH2 * (MgCl2 * 2 THF)o.2_o.3] - der naßchemische Weg zu einem hochreaktiven Titanhydrid [TiH2 * (MgCl2 * 2 THF)0 2_0 3] - the Wet Chemical Route to a Highly Reactive Titanium Hydride  
 Abstract    ohlenforschung, K aiser-W ilhelm -Platz 1, D -45470 M ülheim a. d. Ruhr ein gegan gen am 15. Sep tem b er 1994 M agnesium H ydride, Titanium H ydride, M cM urry-R eaction , T itanium The reaction b etw een catalytically prepared m agnesium hydride (M g H 2*) and [TiCl3(T H F)3] in a m olar ratio o f 1.5:1 in T H F yield s a highly pyrophoric, X -ray am orphous titanium hydride precipitate with the com p osition [TiH 2 -(M gC l2 -2 T H F)0.2-o.3] (2). This novel titanium hydride has been characterized through hydrolysis and iodolysis, as w ell as through therm olysis to Ti* and H 2 in the solid state and in organic solvents. 2 is slightly solub le in T H F and proves itself as an active reagent in a variety o f reactions. 
  Reference    Z. Naturforsch. 50b, 476—4 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0476 
 Volume    50 
75Author    2a 2>, M. =. Cr, M. =. Mo, W. M.Requires cookie*
 Title      
 Abstract    Schem e 1. mination of the 13C,13C coupling constants. For example, 3,5-dimethylcyclobutabenzene [4] (lb) and its tricarbonyl chromium complex [5] 2 b were chosen rather than cyclobutabenzene be­ cause all one-bond couplings can be measured, 
  Reference    Z. Naturforsch. 50b, 483 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0483 
 Volume    50 
76Author    Klaus Angermund, Anette Eckerle, Frank LutzRequires cookie*
 Title    Molecular Modelling: Ein Beitrag zum Verständnis der katalytischen enantioselektiven Hydrovinylierung von Styrol Molecular Modelling: A Contribution to the Understanding of the Catalytic Enantioselective Hydrovinylation of Styrene  
 Abstract    K ohlenforschung. K aiser-W ilhelm -Platz 1, D -45470 M ülheim a. d. Ruhr Z. N aturforsch. 5 0b , 4 8 8 -5 0 2 (1995); ein gegan gen am 24. N o v em b er 1994 H ydrovin ylation. A zap h osp h olen e. N ickel. E nantioselectivity, Styrene The hydrovinylation o f styrene can be catalyzed by the addition o f ph osp h an e-m od ified N i(II) com p ou n d s with high reactivity and en antioselectivity if the azap h osp h olen e 1 is used as P -com p onent o f the catalysts. U n til recently the industrial app lication s o f 1 have been ham pered by its difficult synthesis. To search for easier to syn thesize, but equally w ell cata­ lyzing d erivatives o f 1 a m olecular m odelling study was carried out. B ased on already experi­ m entally tested and structurally characterized azap h osp h olen es a m od el is d e v e lo p ed , which not only lead s to a better understanding o f the catalytic process and but also to a relatively easy way to predict catalytic properties in these system s. U sin g an exten d ed , custom ized valen ce force field several new derivatives o f 1 have been tested. T heir predicted and experi­ m entally determ in ed catalytic properties are in good agreem ent. The X -ray structures o f the p h en yl-sub stituted, m onom eric azaphosph olene 13, which hitherto results in the secon d best catalyst, and o f its precursor 19 are presented. 
  Reference    Z. Naturforsch. 50b, 488 (1995) 
  Published    1995 
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 Identifier    ZNB-1995-50b-0488 
 Volume    50 
77Author    B. Gabor, R. Goddard, S. Holle, P. W. Jolly, C. Krüger, R. Mynott, W. WisniewskiRequires cookie*
 Title    T h e R eaction o f D ien es with [F e (P r z2P ( C H 2) /IP P r /2) ] Species  
 Abstract    D ed ica ted to Prof. D r. Dr. h.c. m u lt G ü n th e r W ilk e o n the o cca sio n o f his 70th birthday The structure of the compounds formed upon reacting Fe(Pr'2P(C H 2)"PPr'2)Cl2 (n = 1-3) and active-Mg with acyclic and cyclic 1,3-, 1,4-and 1,5-dienes depends upon the nature of the diene and upon the length of the methylene-chain bridging the two P-atoms of the biden-tate ligand. For example, isoprene reacts to give either (774-isoprene)2FePPr'2C2H4PPr'2 or (^4-isoprene)Fe(Pr'2PC3H6PPr'2) while the products of the reaction with 1,5-hexadiene are (?75-l-methylpentadienyl)Fe(Pr'2PC2H 4PPr'2)H or (//2,?/2-l,5-hexadiene)Fe(Pr'2PC3H6PPr'2). The crystal structures of the last two compounds have been established by X-ray diffraction. The penultimate species catalyses the linear dimerization of 1,5-hexadiene. 
  Reference    Z. Naturforsch. 50b, 503—513 (1995); received September 15 1994 
  Published    1995 
  Keywords    Iron-Organo Complex, Diene Pentadienyl, X-Ray 
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 Identifier    ZNB-1995-50b-0503 
 Volume    50 
78Author    B. Gyurcsik3, N. Buzásb, T. Gajdab, L. Nagyb, E. Kuzmannc, A. Vértesc, K. BurgerbRequires cookie*
 Title    The Stability and Structure of Complex Species Formed in Equilibrium Reactions of Diethyltin(IV) with N-D-Gluconylamino Acids in Aqueous Solution  
 Abstract    Complex formation equilibria of diethyltin(IV) with five TV-D-gluconylamino acids in aque­ ous solution (I = 0.1 M, NaC104) were studied and the stabilities of the species were deter­ mined by potentiometric titrations. Diethyltin(IV) complexes of a-amino acid derivatives are water-soluble in the physiological pH range, while in the presence of 7V-D-gluconyl-/?-alanine a precipitate is formed, which dissolves with increasing pH. 13C NM R measurements showed that in the /V-D-gluconyl-a-amino acid complexes the ligand is coordinated through its depro-tonated carboxylate oxygen, amide nitrogen and C(2)-hydroxy group, while for the soluble /V-D-gluconyl-/?-alanine complex the ligand is coordinated via the deprotonated carboxylate and C(3)-, C(4)-, C(5)-hydroxy groups. Mössbauer measurements reflected the geometry of the complexes formed. 
  Reference    Z. Naturforsch. 50b, 515—523 (1995); received September 28 1994 
  Published    1995 
  Keywords    Diethyltin(IV), /V-D-Gluconylamino Acid Complexes, Potentiometry, Mössbauer Spectra, NM R Spectra 
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 Identifier    ZNB-1995-50b-0515 
 Volume    50 
79Author    BojanaG. Jeliazkova, JuliaK. PanajotovaRequires cookie*
 Title    Charge Transfer Photochemistry of Bis(8-quinolinolato)copper(II) and Bis(8-quinolinethiolato)copper(II) in Aprotic Solvents  
 Abstract    Charge Transfer Photochemistry, Bis(8-quinolinolato)Cu(II), Bis(8-quinolinethiolato)Cu(II) The photochemistry of bis(8-quinolinolato)Cu(II), Cu(ox)2, and bis(8-quinolinethiolato)-Cu(II), Cu(tox)2, has been studied by continuous photolysis in aprotic solvents. The charge transfer irradiations induce the oxidation of the ligand and the reduction of copper(II) to copper(I). These assignments are supported by EPR data and UV-Vis spectra of the com­ plexes. The photochemical properties of copper(II) complexes are discussed in terms of the population of charge transfer to copper-excited states. Both complexes show solvent-depcnd-ent photochemistry when irradiated in CHC13 and in toluene. The photoproducts of Cu(tox)2 in CHC13 are partially reconverted into the initial complex by thermal reaction, while photo­ reactions of Cu(ox)2 lead to secondary photolytic processes. 
  Reference    Z. Naturforsch. 50b, 524—528 (1995); received October 17 1994 
  Published    1995 
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 Identifier    ZNB-1995-50b-0524 
 Volume    50 
80Author    Kumiko Ohtsu, Kazuhiko Ozutsumi, Makoto Kurihara, Takuji KawashimaRequires cookie*
 Title    Thermodynamics of Complexation of Sodium Ion with 12-Crown-4 and 18-Crown-6 in Pyridine  
 Abstract    The complexation of sodium ion with 1,4,7,10-tetraoxacyclododecane (12-crown-4) and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) has been studied by titration calorimetry in pyridine (P Y) containing 0.1 mol dm-3 (C2H5)4NC 104 as a constant ionic medium at 25 °C. The calorimetric titration data were well explained in terms of the formation of the [Na(12-crown-4)]+, [Na(12-crown-4)2]+, and [Na(18-crown-6)]+ complexes, and their formation constants, reaction enthalpies, and entropies were determined. The formation of [Na(18-crown-6)]+ is much pronounced in PY over yV,7V-dimethylformamide (D M F) and water, and the stability order is PY > DMF > water. The enthalpy values for the formation of [Na(18-crown-6)]+ are all negative in PY, DMF, and water, and increase in the order PY < DMF < water. The complexation is the least exothermic in water, though sodium ion is the most weakly solvated in water. This is because 18-crown-6 is much stabilized in water by forming hydrogen bonds with water molecules. Despite the stronger electron pair-donat­ ing ability of PY than DMF, the complexation is more exothermic in PY than in DMF. This is ascribed to the different solvation number of the sodium ion in P Y and DMF, i.e., the sodium ion is coordinated with a smaller number of solvent molecules in the former solvent than in the latter. 
  Reference    Z. Naturforsch. 50b, 529—535 (1995); received September 12 1994 
  Published    1995 
  Keywords    Thermodynamics of Complexation, Sodium Complexes, 12-Crown-4, 18-Crown-6, Pyridine 
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 Identifier    ZNB-1995-50b-0529 
 Volume    50 
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