Reaktionen von Cyclostibanen (RSb)n [R = (Me3Si)2CH,n = 3; Me3CCH2, n = 4, 5] mit den Übergangsmetallcarbonyl‐Komplexen [W(CO)5(thf)], [CpxMn(CO)2(thf)], [CpxCr(CO)3]2 und [Co2(CO)8]; Cpx = MeC5H4

Reactions of Cyclostibanes, (RSb)_n [R = (Me₃Si)₂CH, n = 3; Me₃CCH₂, n = 4, 5] with the Transition Metal Carbonyl Complexes [W(CO)₅(thf)], [Cp^xMn(CO)₂(thf)], [Cp^xCr(CO)₃]₂, and [Co₂(CO)₈]; Cp^x = MeC₅H₄ (RSb)₃ [R = (Me₃Si)₂CH] reacts with [W(CO)₅(thf)], [Cp^xMn(CO)₂(thf)], or [Co₂(CO)₈] to give [(RSb)₃W(CO)₅] ( 1 ), [RSb{Mn(CO)₂Cp^x}₂] ( 2 ) or [RSbCo(CO)₃]₂ ( 3 ). The reaction of (R′Sb)_n (n = 4, 5; R′ = Me₃CCH₂) with [Cp^xCr(CO)₃]₂ leads to [(R′Sb)₄{Cr(CO)₂Cp^x}₂] ( 4 ); Cp^x = MeC₅H₄, thf = Tetrahydrofuran.     

Ein Natrium‐Oxocobaltat(II)‐Hydroxid: Na5[CoO3]OH ≡ Na10[CoO3]{[CoO3](OH)2}

A Sodium‐Oxocobaltate(II)‐Hydroxide: Na₅[CoO₃]OH ≡ Na₁₀[CoO₃]{[CoO₃](OH)₂} Na₁₀[CoO₃]{[CoO₃](OH)₂} has been obtained from a redox reaction between cobalt metal and CdO in the presence of NaOH and Na₂O at 600 °C (21 d) as red single crystals. The structure has been determined from single crystal data (IPDS‐data, Pnma, Z = 4, a = 988.5(1) pm, b = 1013.9(2) pm, c = 1186.3(2) pm, wR2 = 0.079). Furthermore IR data and aspects of the Madelung part of the lattice energy are presented.     

Die ersten Oxocobaltate(II) mit zweikernigem Anion: Rb2Na4[Co2O5] und K2Na4[Co2O5]

The First Oxocobaltate(II) with Dinuclear Anion: Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] By heating of well ground mixtures of the binary oxides [A₂O, Na₂O, ?CoO”?, A:Na:Co = 1.00:2.00:1, (A = K, Rb); Ag-tube, 600°C, 14 d] we obtained Rb₂Na₄[Co₂O₅] and K₂Na₄[Co₂O₅] rough, transparent, red single crystals. We find a new type of structure with the anion [O₂CoOCoO₂]^6?. Space group P4₂/mnm; a = 634.4 pm, c = 1030.3 pm, Z = 2 (A = K) a = 647.6 pm, c = 1021.1 pm, Z = 2 (A = Rb); four-circle diffractometer data; MoKα -radiation; 360 from 364 I₀(hkl), R = 4.34%, R_w = 3.54% (A = K); 361 from 366 I₀(hkl), R = 6.54%, R_w = 2.70% (A = Rb). The anion is planar, the CN of Co is 3. The Madelung Part of Lattice Energy, MAPLE, and Effective Coordination Numbers, ECoN, are calculated and discussed.     

Ein Natrium‐Oxocobaltat(II)‐Sulfat: Na8[CoO3][SO4]2

A Sodium Oxocobaltate(II) Sulfate: Na₈[CoO₃][SO₄]₂ Na₈[CoO₃][SO₄]₂ has been obtained from a redox reaction between cobalt metal and CdO in the presence of Na₂SO₄ and Na₂O at 550 °C (15 d) as red single crystals. The structure has been determined from single crystal data (IPDS‐data, T = 170 K, Cmcm, Z = 4, a = 806.88(9) pm, b = 2232.1(3) pm, c = 705.97(9) pm, R_all = 0.047). Magnetic properties and spectroscopic investigations are reported and discussed within the Angular‐Overlap‐Model.     

[Co4P2(PtBu2)2(CO)8] und [{Co(CO)3}2P4tBu4] aus Co2(CO)8 und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co₄P₂(P^tBu₂)₂(CO)₈] and [{Co(CO)₃}₂P₄^tBu₄] from Co₂(CO)₈ and ^tBu₂P–P=P(Me)^tBu₂ Co₂(CO)₈ reacts with ^tBu₂P–P=P(Me)^tBu₂ yielding the compounds [Co₄P₂(P^tBu₂)₂(CO)₈] ( 1 ) and [{η^2tBu₂P=P–P=P^tBu₂}{Co(CO)₃}₂] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ₂‐bridged by ^tBu₂P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)₃ units is η²‐coordinated to the terminal P₂ units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.     

Synthesen und Strukturen neuer amido- und imidoverbrückter Cobaltcluster: [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] (1), [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] (2), [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] (3) und [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] (4)

Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] (1), [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] (2), [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] (3), and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li₂NPh leads to an amido-bridged multinuclear complex [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] ( 3 ) and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.     

Neue arsinidenverbrückte Mehrkern-Clusterkomplexe des Ag und Au. Die Kristallstrukturen von [Ag14(AsPh)6Cl2(PR3)8], (PR3 = PEt3, PMenPr2, PnPr3), [M4(As4Ph4)2(PR3)4], (M = Ag,PR3 = PEt3, PnPr3; M = Au,PR3 = PnPr3), [Au10(AsPh)4(PhAsSiMe3)2(PnPr3)6]

New Arsinidene-bridged Multinuclear Cluster Complexes of Ag and Au. The Crystal Structures of [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃, PMeⁿPr₂, PⁿPr₃), [M₄(As₄Ph₄)₂(PR₃)₄], (M = Ag, PR₃ = PEt₃, PⁿPr₃; M = Au, PR₃ = PⁿPr₃), [Au₁₀(AsPh)₄(PhAsSiMe₃)₂(PⁿPr₃)₆] The reaction of AgCl with PhAs(SiMe₃)₂ in presence of tertiary phosphines (PR₃) leads to arsinidene-bridged silver clusters with the composition [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃ 1 , PMeⁿPr₂ 2 , PⁿPr₃ 3 ). Further it is possible to obtain the multinuclear complexes [Ag₄(As₄Ph₄)₂(PR₃)₄], (PR₃ = PEt₃ 4 , PMeⁿPr₂ 5 ). In analogy to that [PMe₃AuCl] reacts with PhAs(SiMe₃)₂ and PⁿPr₃ to form the compound [Au₄(As₄Ph₄)₂(PⁿPr₃)₄] 6 , which is isostructurell to 4 and 5 . The gold cluster [Au₁₀(AsPh)₄(PhAsSiMe₃)₂(PⁿPr₃)₆] 7 was obtained from the same solution. The structures were characterized by X-ray single crystal structure analysis. (Crystallographic data see “Inhaltsübersicht”)     

[Co7(μ4‐O)2(O2C–CH3)8(NCO)2(HNPEt3)4] · 2 OEt2, ein siebenkerniger Komplex mit vier‐, fünf‐ und sechsfach koordinierten Cobalt‐Atomen

[Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂(HNPEt₃)₄] · 2 OEt₂, a Seven Nuclearity Complex with Four, Five, and Sixfold Coordinated Cobalt Atoms The title compound was prepared from cobalt(II) acetate with Me₃SiNPEt₃ at 180 °C and subsequent crystallization from diethylether to give blue, moisture sensitive single crystals, which were characterized by a crystal structure determination. Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1544.0(1), b = 1522.1(2), c = 1702.0(1) pm, β = 103.911(10)°, R = 0.0490. [Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂ · (HNPEt₃)₄] has a centrosymmetric cluster‐like structure in which the octahedrally coordinated central cobalt atom is connected with the remaining six cobalt atoms via two μ₄‐oxygen atoms as well as via four bridging acetato groups to form a Co(Co)₆ octahedral skeleton. Four of the peripheric cobalt atoms have a distorted trigonal‐bipyramidal coordination sphere, the other two cobalt atoms are tetrahedrally coordinated. The latter are connected with the nitrogen atoms of the cyanato groups.     

Das erste quinquinäre Oxoaurat(I) K6Na[IO6][AuO]2 = K6[NaIO6][AuO2/2]2 [1]

Inhaltsübersicht. Bei Versuchen zur Darstellung unbekannter Phasen im System A/Au/I/O (mit A = Alkalimetall) entstanden durch Erhitzen eines Gemenges (2,2 K₂O + 1,0 NaIO₄; Au-Rohr; 700°C, 59 d) farblose, transparente Einkristalle von K₆NaAu₂IO₈, das nach Einkristalldaten (Vierkreisdiffraktometerdaten, 2465 I_o(hkl), AgKα, R = 6,8% und R_w = 5,6%) monoklin in P2/c mit a = 707,4 pm; b = 977,3 pm; c = 1199,4 pm; β = 122,9°; Z = 2 kristallisiert. Charakteristisch sind die hier erstmals gefundenen, HgO-analogen Zickzackketten [AuO_2/2] längs [001]. Daneben prägen, den NaIO₆-Teil der Struktur betreffend, Ketten aus [IO₆]-Oktaeder, über Na in prismatischer Koordination verknüpft, den Aufbau. The First Quinquinary Oxoaurate(I). K₆Na[IO₆][AuO]₂ = K₆[NaIO₆][AuO_2/2]₂ Attempting to synthesize unknown phases in the system A/Au/I/O by heating a mixture of K₂O and NaIO₄ (K: Na = 2.2:1.0, sealed gold tube, 700°C) we obtained colourless, transparent single crystals of K₆NaAu₂IO₆, a new type of Oxoaurate(I). According to single crystal data K₆NaAu₂IO₈ crystallizes in a monoclinic form with a = 707.4 pm, b = 977.3 pm, c = 1199.4 pm β = 122.9° (Z = 2, space group P2/c). Essential part of the structure are chains NaIO₆ and zigzag chains AuO_2/2, both along [001]. The Madelung part of the lattice energy, MAPLE, and effective coordination numbers, ECoN, are calculated and discussed.     

Polyol-Metall-Komplexe. XIII [1]. Na2[Be(C4H6O3)2] · 5H2O und Na2[Pb(C4H6O3)2] · 3H2O – zwei homoleptische Bis-polyolato-metallate mit Beryllium und mit Blei

Polyol Metal Complexes. XIII. Na₂[Be(C₄H₆O₃)₂] · 5H₂O and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O – Two Homoleptic Bis Polyolato Metallates with Beryllium and with Lead Na₂[Be(C₄H₆O₃)₂] · 5H₂O ( 1 ) and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O ( 2 ) crystallize from concentrated, alkaline aqueous solutions. The polyol anhydroerythritol is deprotonated twice in the mononuclear, homoleptic complex anions. The preference of beryllium for the binding of cis-furanoid diols is shown. In 2 , a stereochemically active lone pair at the central atom is the reason for the construction of low dimensional aggregates from three plumbate and three sodium ions.     

Über die quasi-binären Systeme NaNO2/Na2O und NaCN/Na2O. Phasendiagramme und Natrium-Ionenleitung in Na3O(NO2) und Na3O(CN)

On the Quasi-Binary Systems NaNO₂/Na₂O and NaCN/Na₂O. Phase Diagrams and Sodium Ion Conductivity of Na₃O(NO₂) and Na₃O(CN) Measurements of the electrical conductivities of Na₃O(NO₂) and Na₃O(CN) show sharp increases in conductivity at temperatures between 200° and 250°C, According to the phase diagrams of the quasi-binary systems NaNO₂/Na₂O and NaCN/Na₂O this is not an effect established by fusion. It seems to be a consequence of a “melting” of the sodium sublattice or the rotational disorder of complex anions.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Die Kristallstruktur eines polynuklearen Co(II)-Komplexes in Cs2[Co3(N3)8]

Cs₂[Co₃(N₃)₈] crystallizes monoclinic,a=1 123.8 (3),b=568.4 (2),c=1 542.6 (4) pm, =107.37 (2)°, space group P2₁/n,Z=2. The crystal structure was determined by single crystal X-ray diffraction,R _w=0.069. Coatoms are coordinated octahedrally to six azide groups and form polynuclear complexes of composition [Co₃(N₃)₈]^2–. The complex anions share edges and are connected to infinite chains running along theb-axis direction. Cesium is irregularly surrounded by azide groups.

     

N2O在Au/Co3O4和Au/ZnCo2O4催化剂上的分解反应

通过调变HAuCl₄溶液的pH值和Au负载量,用沉积-沉淀法制备了一系列Au/Co₃O₄催化剂,并采用AES、BET、XRD、SEM、XPS和H₂-TPR等技术对催化剂的结构和组成进行了表征,考察了制备条件对其在有氧气氛中催化N₂O分解反应性能的影响规律,得到了催化剂最佳制备条件:HAuCl₄溶液pH值为9,Au负载量为0.29%。催化测试结果表明:虽然ZnCo₂O₄的催化活性优于Co₃O₄,但0.31%Au/ZnCo₂O₄的活性和稳定性低于0.29%Au/Co₃O₄。500℃、在含氧气氛中连续反应10 h, 两者均可完全分解N₂O,但在含氧、含水气氛中0.29%Au/Co₃O₄和0.31%Au/ZnCo₂O₄上的N₂O转化率分别为92%和63%。究其原因,发现Au/Co₃O₄中Au和Co组分间存在协同效应,而Au/ZnCo₂O₄中Au和Co组分间则没有协同效应。     

Asymmetric salt effects on anion/cation reactions: A comparative study of the [Fe(CN)6]4− + [Co(NH3)5pz]3+ and [Ru(NH3)5pz]2+ + [Co(C2O4)3]3− reactions

The kinetics of electron transfer reactions between [Fe(CN)₆]^4? and [Co(NH₃)₅pz]³⁺ and between [Ru(NH₃)₅pz]²⁺ and [Co(C₂O₄)₃]^3? was studied in concentrated salt solutions (Na₂SO₄, LiNO₃, and Ca(NO₃)₂). An analysis of the experimental kinetic data, k_obs, permits us to obtain the true (unimolecular) electron transfer rate constants corresponding to the true electron transfer process (precursor complex → successor complex), k_et. The variations of both, k_obs and k_et, with salt concentrations are opposite for these reactions. These opposite tendencies can be rationalized by using the Marcus–Hush treatment for electron transfer reactions. The conclusion is that the negative salt effect found for the first reaction ([Fe(CN)₆]^4? + [Co(NH₃)₅pz]³⁺) is due to the increase of the reaction and reorganization free energies when the concentration of salt increases. In the case of the second reaction ([Ru(NH₃)₅pz]²⁺ + [Co(C₂O₄)₃]^3?), the positive salt effect observed is caused by the fact that the driving force becomes more favorable when the concentration of salt increases. Thus, it is shown that for anion/cation electron transfer reactions the kinetic salt effect depends on the charge sign of the oxidant (and the reductant). © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 81–89, 2005