Zur kenntnis der cyclopentadienyl-nitrosyl-carbonyl-isonitril-komplexe der VI. Und der cyclopentadienyl-dicarbonyl-isonitril-komplexe der VII. Nebengruppe

The nitrosylcarbonylisonitrile complexes η⁵-C₅H₅M(NO)(CO)CNR (R = Me for Cr, Mo, W; R = Et, SiMe₃, GeMe₃, SnMe₃ for Mo) are formed by treatment of the nitrosylcarbonylcyanometalates Na[η⁵-C₅H₅M(NO)(CO)CN] with [R₃O]BF₄ (R = Me, Et), Me₃SiCl, Me₃GeCl or Me₃SnCl. The isoelectronic dicarbonylisonitrile compounds η⁵-C₅H₅Mn(CO)₂CNR (R = SiMe₃, GeMe₃, SnMe₃, PPh₂, AsMe₂) and η⁵-C₅H₅Re(CO)₂CNAsMe₂ are obtained by analogous reactions of Na[η⁵-C₅H₅M(CO)₂CN] (M = Mn, Re) with Me₃ECl (E = Si, Ge, Sn), Ph₂PCl and Me₂AsBr.With phosgene the anionic complexes Na[η⁵-C₅H₅M(CO)₂CN] (M = Mn, Re) can be transformed into the new carbonyldiisocyanide-bridged dinuclear complexes η⁵-C₅H₅M(CO)₂CN-C(O)-NC(OC)₂M-η⁵-C₅H₅. Finally, the reactions of η⁵-C₅H₅M(NO)(CO)CNMe (M = Cr, Mo, W) with NOPF₆, leading to the cationic dinitrosylisonitrile complexes [η⁵-C₅H₅M(NO)₂CNMe]⁺, are described.     

Metallorganische Verbindungen der Lanthanoide. 111. Synthese und Charakterisierung kationischer Metallocen-Komplexe der Lanthanoide. Röntgenstrukturanalyse von [CpYb(THF)2][BPh4]

Organometallic Compounds of the Lanthanoids. 111. Synthesis and Characterization of Cationic Metallocene Complexes of the Lanthanoides. X-Ray Crystal Structure of [Cp Yb(THF)₂][BPh₄] Cationic organolanthanoide compounds [(C₅H₄R)₂Sm(THF)₂][BPh₄] (R = ^tBu ( 1 ), SiMe₃ ( 2 )), [PyrSm(THF)][BPh₄] ( 3 ) (Pyr* = NC₄H₂^tBu₂-2,5), [CpLn(THF)₂][BPh₄] (Cp* = C₅Me₅; Ln = Y ( 4 ), Yb ( 5 )), and [(C₅Me₄Et)₂ Ln(THF)₂][BPh₄] (Ln = Y ( 6 ), Sm ( 7 )) have been synthesized by oxidation of the divalent metallocenes [(C₅H₄R)₂Sm(THF)₂] (R = ^tBu, SiMe₃), [PyrSm(THF)], [CpYb(THF), and [(C₅Me₄Et)₂Sm(THF)] with Ag[BPh₄] and by protolysis of the lanthanoide alkyls [CpYMe(THF)], [CpYbCH(SiMe₃)₂], and [(C₅Me₄Et)₂LnCH(SiMe₃)₂] (Ln = Y, Sm) by [NEt₃H][BPh₄]. The ¹H- and ¹³C-NMR spectra of the new compounds are discussed. 5 crystallizes in the space group P2₁/c with a = 10.604(7), b = 21.749(3), c = 19.124(4) Å, β = 96.47(4)°, Z = 4 and V = 4383(3) ų (R = 0.0291 for 8517 observed reflections with F_o ≥ 4σ (F_o).     

1H- und 13C-NMR.-Spektroskopie der Nonadride

¹H- and ¹³C-NMR. Spectroscopy of the Nonadrides The ¹H- and ¹³C-NMR. spectra of the nonadrides glaucanic acid ( 1 ), glauconic acid ( 2 ), heveadride ( 3 ), byssochlamic acid ( 4 ), scytalidin ( 5 ), rubratoxin A ( 6 ), and rubratoxin B ( 7 ) have been measured. Partial decoupling experiments permitted assignment of the majority of the signals.     

Metallorganische Verbindungen der Lanthanoide. 93 [1]. Tetramethylcyclopentadienyl-Komplexe ausgewählter 4f-Elemente

Organometallic Compounds of the Lanthanides. 93. Tetramethylcyclopentadienyl Complexes of Selected 4f-Elements The trichlorides of lanthanum, neodymium, samarium, and terbium react with Na(C₅Me₄H) in THF to yield the homoleptic complexes Ln(C₅Me₄H)₃ [Ln = La ( 1a ), Nd ( 1b ), Sm ( 1c ), Tb ( 1d )]. On the other hand the reactions of HoCl₃, TmCl₃, and LuCl₃ with Na(C₅Me₄H) result only with formation of the dicyclopentadienyl complexes (C₅Me₄H)₂LnCl(THF) [Ln = Ho ( 2e ), Tm ( 2f ), Lu ( 2h )]. The metallocenes (C₅Me₄H)₂Ln(THF)₂ [Ln = Sm ( 3c ), Yb ( 3g )] are obtained by the reactions of LnI₂ (Ln = Sm, Yb) with Na(C₅Me₄H). The ¹H- and ¹³C-NMR spectra as well as the X-ray crystal structure of the triscyclopentadienyl complexes 1 a and 1 c are discussed.     

Komplexchemie P-reicher Phosphane und Silylphosphane. VIII. Zur unterschiedlichen Tendenz der Bildung von Chromcarbonyl-Komplexen silylierter-alkylierter Phosphane und Diphosphane

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VIII. Concerning the Different Tendencies of Silylated and Alkylated Phosphanes and Diphosphanes to Form Chromium Carbonyl Complexes The influence of the substituents Me₃Si tBu and Me in phosphanes and diphosphanes on the formation of complex compounds with Cr(CO)₅THF is investigated. tBu(Me₃Si)P? P(SiMe₃)₂ 1 and (tBu)₂P? P(SiMe₃)₂ 2, resp., react with Cr(CO)₅THF 4 at ?18°C by coordinating Cr(CO)₅ to the P(SiMe₃)₂ group to give tBu(Me₃Si)P? P^IV(SiMe₃), · Cr(CO)₅ 1 a, tBu(Me₃Si)P^IV? P^IV(SiMe₃)₂ · Cr(CO)₄ 1b and (tBu)₂P? P^IV(SiMe₃)₂ · Cr(CO)₅ 2a . In the reaction of 1 with 4 using a molar ratio of 1:2 at first 1 a is formed which reacts on to yield completely 1 b. In a mixture of the dissolved compounds (Me₃Si)₃P 5, (tBu)₃P 6 and (tBu)₃P? P(SiMe₃)₂ 2 only 5 and 6 react with Cr(CO)₅THF yielding (Me₃Si)₃P · Cr(CO)₅ and (tBu)₃P · Cr(CO)₅, but 2 does not yet react. In a solution of (Me₃Si)₃P 5, P₂Me₄ 7 and (Me₃Si)₂P? PMe₂ 3 only 5 and 7 react with Cr(CO)₅THF (0.25 to 1.5 equivalents with respect to 3) to give (Me₃Si)₃P · Cr(CO)₅, P₂Me₄ · Cr(CO)₅ and P₂Me₄ · 2Cr(CO)₅. The formation of complexes with Cr(CO)₅THF of the phosphanes 5 and 6 is clearly favoured as compared to the silylated diphosphanes 2 and 3 (not to P₂Me₄); the PR₂ groups (R = tBu, Me in 2 or 3 ) don't have a strong influence.     

Komplexchemie P-reicher Phosphane und Silylphosphane. IV. Bildung und Struktur der Chromcarbonylkomplexe des Tris(di-tert-butylphospha)heptaphosphanortricyclans, (t-Bu2P)3P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. IV. Formation and Structure of the Chromium Carbonyl Complexes of Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu₂P)₃P₇ The reaction of (t-Bu₂P)₃P₇ 1 with Cr(CO)₅ · THF in a molar ratio of 1:1 yields yellow crystals of (t-Bu₂P)₃P₇[Cr(CO)₅] 2 having the Cr(CO)₅ group coordinated to a P^b atom (basal) of the three membered ring. With a molar ratio of 1:2 compounds 2 , (t-Bu₂P)₃P₇[Cr(CO)₅]₂ 3 , (t-Bu₂P)₃P₇[Cr(CO)₅][Cr(CO)₄] 4 and (t-Bu₂P)₃P₇[Cr(CO)₄]₂ 5 were obtained. In 3 (yellow crystals) one Cr(CO)₅ group is linked to a P^b atom, the other one to an exocyclic P^exo atom. On irradiation 3 loosing one CO group generates 4 (orange red crystals) with an unchanged Cr(CO)₅ group linked to the Pb atom and a five membered chelate-like ring containing an apical Pa atom, two equatorial P^a atoms, one P^exo atom and the Cr atom of the carbonyl group. Compound 5 (orange red crystals) contains two such five membered rings. (t-Bu₂P)₃P₇[Cr(CO)₄]₃ 6 (red needles) is formed with Cr(CO)₅ · THF in a molar ratio of 1 : 1. However, even with higher amounts of Cr(CO)₅ · THF and after extended reaction times, only 6 is formed; no further Cr carbonyl group could be attached to the P skeleton. With Cr(CO)₅ · NBD in a molar ratio of 1 : 1, (t-Bu₂P)₃P₇[Cr(CO)₄] 7 is produced from 1, and 5 with a molar ratio of 2 : 1. As in 4, the Cr(CO)₄ group in 7 (orange crystals) participates in a five membered chelate-like ring. It was not possible to generate 6 from 5 with an excess of Cr(CO)₄ · NBD and with extended reaction times. The molecular structures of the compounds were identified by investigating the ³¹P[¹H] NMR spec-tra and considering especially the coordination shift, and by crystal structure determinations of 2 and 4. Compound 2 crystallizes in the space group PI (no.2) with a = 1566.2(4) pm, b = 2304.1(5) pm, c = 1563.3(4) pm,α = 95.57(3)°, β = 108.79(3)°, γ = 109.82(4)° and Z = 4 formula units in the elementary cell. Compound 4 crystallizes in the space group P 2₁ /n (no. 14) with a = 1416.6(5) pm, b = 2573.6(5) pm, c = 1352.9(4) pm,β = 99.17(5)° and Z = 4 formula units in the elementary cell.     

Metallkomplexe mit anionischen Liganden von Elementen der 4. Hauptgruppe. XI. Substitutionsreaktionen der Trichlorgermid- und Trichlorstannid-Ionen an Metalltrifluorphosphin-Komplexen

Metal Complexes with Anionic Ligands of Main Group IV Elements. XI. Substitution Reactions of Trichlorogermide and Trichlorostannide Ions with Metaltrifluorophosphine Complexes The photochemical reactions of [SnCl₃]^? in THF with the metal(0)-trifluorophosphine complexes of Ni, Fe, and Mo result in [Ni(PF₃)₃SnCl₃]^?, [Fe(PF₃)₃(SnCl₂]^?, and [Mo(PF₃)₅SnCl₃]^?. [GeCl₃]^?, in substitution reactions not as reactive as [SnCl₃]^?, does react under similar conditions with Fe(NO)₂(PF₃)₂ only, to yield [Fe(NO)₂(PF₃)GeCl₃]^?. With CpMn(PF₃)₃ (Cp = h⁵-C₅H₅) by the intermediatly formed CpMn(PF₃)₂THF both substitution derivatives [CpMn(PF₃)₂ECl₃]^? (E = Ge, Sn) are found. The metallate(0) complexes are isolated as [As(C₆H₅))₄]⁺- and [N(C₂H₅)₄]⁺ -salts; the i.r.- and ¹⁹F-n.m.r.-spectra are reported.     

Zur Kenntnis der Organophosphorverbindungen. XV. Darstellung und Reaktionen von Trimethylsilylestern der Phosphinsäuren

On Organophosphorus Compounds. XV. Preparation and Reactions of Trimethylsilyl Esters of Phosphinic Acids Trimethylsilylesters of Phosphinic acids R₂P(X)YSi(CH₃)₃ (R ? CH₃, C₂H₅, C₃H₇, t?C₄H₉, C₆H₅; X, Y ? O, S) were prepared by 7 different methods as in some cases easily hydrolysable but thermally remarkably stable compounds. The properties and some reactions of these substances are reported, their structures confirmed by IR? as well as ¹H- and ³¹P-NMR-spectroscopy. Dimethylsilylen-bis(phosphinic acid esters) were obtained according to \documentclass{article}\pagestyle{empty}\begin{document}$ 2{\rm R}_{2} {\rm P(\rm X)\rm ONH}_{4} + {\rm R}_{\rm 2} {\rm SiCl}_{2} \to 2{\rm E NH}_{4} {\rm Cl + R}_{2} {\rm P(X) - O - SiR}_{2} - {\rm O - P(X)R}_{2} ({\rm R = CH}_{3};{\rm X = O,S}) $\end{document}.     

Metallorganische Verbindungen der Lanthanoide. 155 [1] Synthese und Charakterisierung neuer Lanthanoidocen‐Komplexe mit silylierten Cyclopentadienylliganden

Organometallic Compounds of the Lanthanides. 155 [1] Synthesis and Characterization of New Lanthanocene Complexes containing Silylated Cyclopentadienyl Ligands The trichlorides of yttrium, samarium, and lutetium react with two equiv. of K[C₅H₄SiEt₃] ( 1 ) to form the dimeric compounds [(η⁵‐C₅H₄SiEt₃)₂LnCl]₂ (Ln = Y ( 2 ), Sm ( 3 ), Lu ( 4 )). These react with one equiv. of methyllithium to give the corresponding dimeric lanthanocenemethyl complexes [(η⁵‐C₅H₄SiEt₃)₂LnMe]₂ (Ln = Y ( 5 ), Sm ( 6 ), Lu ( 7 )). The reaction between samarium trichloride and lutetium trichloride, respectively with two equiv. of K[1, 3‐C₅H₃(SiMe₃)₂] followed by one equiv. of methyllithium results in the formation of the monomeric methyl complexes [η⁵‐1, 3‐C₅H₃(SiMe₃)₂]₂LnMe(THF) (Ln = Sm ( 8 ), Lu ( 9 )). The new compounds have been characterized by elemental analysis, mass spectrometry, ¹H‐ and ¹³C{¹H} NMR spectroscopy, as well as 1 — 7 by single crystal X‐ray structure analysis.     

Über die Chemie der Oberfläche des Titandioxids. III. Reaktionen der basischen Hydroxylgruppen auf der Oberfläche

Adsorption of various acids on anatase of high surface area was studied. Phosphoric, arsenic, sulphuric and acetic acid are specifically adsorbed; hydrochloric and perchloric acid are not adsorbed. Phosphate ions are bound on the TiO₂ surface also from NaH₂PO₄ and Na₂HPO₄ solutions; sodium ions are adsorbed at the same time. OH^? ions on the surface are replaced by anions such as H₂PO in these reactions. The bonding of adsorbed phosphate ions is not purely ionic. Infrared spectra show that adsorbed acetic acid is bound as acetate. NO₂ reacts with the basic OH^? ions undergoing disproportionation; OH^? ions are replaced by NO ions. Phophoric acid adsorption corresponded always to half the total OH population on five different TiO₂ samples. The TiO₂ surface is not completely covered by OH groups. The maximum coverage is ca. 7.5 μMol OH/m².     

Metallorganische Verbindungen der Lanthanoide. 113. [(tert-Butylcyclopentadienyl)(cyclopentadienyl)dimethylsilan]-Komplexe ausgewählter Lanthanoide

Organometallic Compounds of the Lanthanides. 113. [(tert-Butylcyclopentadienyl)(cyclopentadienyl)dimethylsilane] Complexes of selected Lanthanides The reaction of [Me₂Si(C₅H₄)(tBuC₅H₃)]Li₂ with LnCl₃ (Ln = Y, Nd, Sm, Lu) in THF results in the formation of the chiral, dimeric complexes [Me₂Si(C₅H₄)(tBuC₅H₃)]Ln(μ-Cl)₂Li(THF)(Et₂O) [Ln = Y ( 1 ), Nd ( 2 ), Sm ( 3 ), Lu ( 4 )]. The ¹H-, ¹³C-NMR- and the mass spectra of the new compounds as well as the X-ray crystal structures of 2 a and 3 a were discussed.     

Untersuchungen an Polyhalogeniden. XVI. Darstellung und Kristallstrukturen der Bipyridiniumpolyiodide Bipy · HIn mit n = 3, 5 und 7

Studies on Polyhalides. 16. Preparation and Crystal Structures of Bipyridiniumpolyiodides Bipy · HI_n with n = 3, 5, and 7 With simply protonated α,α′-Bipyridyl Bipy · H⁺ a triiodide Bipy · HI₃, a pentaiodide Bipy · HI₅ and a heptaiodide Bipy · HI₇ may be prepared in the presence of iodide ions I^? and dependent of the iodine I₂ content. Bipyridiniumtriiodide C₁₀H₉N₂I₃ crystallizes at room temperature monoclinically in P2₁/n with a = 1 122.8(1) pm, b = 1 072.7(1) pm, c = 1 200.2(3) pm, β = 98.02(2)° and Z = 4. The crystal structure is built up from mixed cationic and anionic layers. Bipyridiniumpentaiodide C₁₀H₉N₂I₅ crystallizes at room temperature monoclinically in P2₁/c with a = 887.3(5) pm, b = 2 527.9(12) pm, c = 830.7(3) pm, β = 106.78(5)° and Z = 4. The crystal structure contains triiodide ions I₃^? till now uniquely connected by iodine molecules I₂ in a trigonal planar way. Bipyridiniumheptaiodide C₁₀H₉N₂I₇ crystallizes at room temperature triclinically in P&1macr; with a = 713.1(3) pm, b = 1 007.9(3) pm, c = 1 464,8(4) pm, α = 81.07(3)°, β = 89.92(3)°, γ = 82.77(3)° and Z = 2. The crystal structure contains a V-shaped pentaiodide ion I₅^? completed by an iodine molecule I₂ to a trigonal pyramidally shaped heptaiodide ion I₇^? and at the same time connected to a zigzag chain.     

Zur kenntnis der chemie der metallcarbonyle und der cyanokomplexe in flüssigem ammoniak : XXXIII. Über die darstellung neuer carbamoylcarbonyl-komplexe aus bekannten und neuen kationischen carbonylverbindungen des mangans und rheniums

The covalent carbamoyl carbonyl compounds Re(CO)₅COHN₂, cis-M(CO)₄(L)CONH₂, M(CO)₃(L)₂CONH₂ and M(CO)₃(D)CONH₂ (M = Mn, Re; L = PPh₃, PEt₃; D = bipy, phen) are formed by reactions of the cationic complexes [Re(CO)₆]⁺, [M(CO)₅L]⁺, [M(CO)₄L₂]⁺ and [M(CO)₄D]⁺ (M = Mn, Re; L = PPh₃, PEt₃; D = bipy, phen) with liquid NH₃ with concomitant deprotonation: [M(CO)_6?nL_n]⁺ + 2 NH₃ → M(CO)_5?nL_nCONH₂ + NH₄⁺ (n = 0, 1, 2) and [M(CO)₄D]⁺ + 2 NH₃ → M(CO)₃(D)CONH₂ + NH₄⁺ The stability of the above-mentioned carbamoyl carbonyl complexes increases from the penta- to the tetra- to the tri-carbonyl derivatives. In all cases the rhenium compounds are much more stable than the corresponding manganese complexes. Whereas the carbamoyl compound Re(CO)₄(PEt₃)CONH₂ can be isolated by reaction of [Re(CO)₅PEt₃]⁺ with NH₃, the corresponding manganese complex undergoes Hofmann degradation of amides even at ?70°C to form HMn(CO)₄PEt₃ and NH₄NCO. The IR and some mass and ¹H NMR spectra of the new hexacoordinated carbamoyl carbonyl complexes are discussed and the reactions of these compounds with liquid NH₃, HCl and CH₃OH are described.     

Zur Kenntnis der Chemie der Silazane. IV. Über ein Sulfurylphosphazo-silazan

Trichlorophosphazo-sulphurylchloride. Cl₃P?N? SO₂Cl, reacts with heptamethyldisilazane to yield the Si? N? P compound (I) formulated in ?Inhaltsübersicht”?. (I) reacts with PCl₅ or C₆H₅? PCl₄ forming the known 2,2,2,4,4,4-hexachloro-1,3-di-methylcyclo-diphosphazane(II), accompanied by the compound Cl₃P?N? SO₂Cl and C₆H₅? PCl₂?N? SO₂Cl, respectively, which were detected by means of ³¹P-NMR spectroscopy.     

Die Möglichkeiten der Anwendung der Wechselstrompolarographie auf die Messung der Geschwindigkeitskonstanten

Zusammenfassung Die Wechselstrompolarographie ist für die Messung der Geschwindigkeitskonstanten der Elektrodenprozesse im Bereich von 5·10^–3–5·10^–2 cm sec^–1 anwendbar. Das bestätigen auch die Ergebnisse, die für ein Modellsystem erhalten wurden. Experimentell wurde die Anwendbarkeit der Methode am Redoxsystem [CrCl₂(H₂O)₄]⁺–[CrCl₂(H₂O)₄] in sauren 4–9n-LiCl-Lösungen nachgeprüft, und zwar durch den Vergleich der Resultate mit den Ergebnissen der Messungen derFaraday-impedanz und der Methode der überlagerten Spannung.

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Application of alternating current polarography for the measurement of rate constants

The method of alternating current polarography is known to be applicable to the measurement of rate constants of electrode reactions within the range of 5·10^–3 to 5·10^–2 cm sec^–1. This follows also from the results obtained with model systems. The applicability of the method has been studied in the redox-system [CrCl₂(H₂O)₄]⁺–[CrCl₂(H₂O)₄] in acid solutions of 4N to 9N LiCl. The results were compared with those obtained by measuring the faradaic impedance and with the results of the method of periodically changed rectangular voltage.

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Mit 7 Abbildungen     

Azimine IV. Kinetik und Mechanismus der thermischen Stereoisomerisierung von 2,3-Diaryl-1-phthalimido-aziminen

Azimines IV. Kinetics and Mechanism of the Thermal Stereoisomerization of 2,3-Diaryl-1-phthalimido-azimines¹) Mixtures of (1E, 2Z)- and (1Z, 2E)-2-phenyl-1-phthalimido-3-p-tolyl-azimine ( 3a and 3b , resp.) and (1E, 2Z)- and (1Z, 2E)-3-phenyl-1-phthalimido-2-p-tolylazimine ( 4a and 4b , resp.) were obtained by the addition of oxidatively generated phthalimido-nitrene (6) to (E)- and (Z)-4-methyl-azobenzene ( 7a and 7b , resp.). Whereas complete separation of the 4 isomers 3a, 3b, 4a and 4b was not possible, partial separation by chromatography and crystallization led to 5 differently composed mixtures of azimine isomers. The spectroscopic properties of these mixtures (UV., ¹H-NMR.) were used to determine the ratios of isomers in the mixtures, and served as a tool for the assignment of constitution and configuration to those isomers which were dominant in each of these mixtures, respectively. Investigation of the isomerization of the azimines 3a, 3b, 4a and 4b within the 5 mixtures at various concentrations by ¹H-NMR.-spectroscopy at room temperature revealed that only stereoisomers are interconverted ( 3a ? 3b; 4a ? 4b) and that the (1E, 2Z) ? (1Z, 2E) stereoisomerization is a unimolecular reaction. These observations exclude an isomerization mechanism via an intermediate 1-phthalimido-triaziridine (2) or via dimerization of 1-phthalimido-azimines (1) , respectively. The 3-p-tolyl substituted stereoisomers 3a and 3b isomerized slightly slower than the 3-phenyl substituted ones 4a and 4b , an effect which is consistent with the assumption that the rate determining step of the interconversion of (1E, 2Z)- and (1Z, 2E)-1-phthalimido-azimines (1a ? 1b) is the stereoisomerization of the stereogenic center at N(2), N(3), either by inversion of N(3) or by rotation around the N(2), N(3) bond. The total isomerization process is assumed to occur via the thermodynamically less stable (1Z, 2Z)- and (1E, 2E)-isomers 1c and 1d , respectively, as intermediates in undetectably low concentrations which stay in rapidly established equilibria with the observed, thermodynamically more stable (1E, 2Z)- and (1Z, 2E)-isomers 1a and 1b , respectively. At higher temperatures, the azimines 3 and 4 are transformed into N-phenyl-N,N′-phthaloyl-N′-p-tolyl-hydrazine (8) with loss of nitrogen.     

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyano-Komplexe in flüssigem ammoniak : XL. Über die Reaktion kationischer Cyclopentadienyl-carbonyl-nitrosyl-Komplexe des Mangans und Rheniums mit flüssigem Ammoniak

The reactions of the cationic complexes [CpMn(CO)₂NO]⁺, [MeCpMn(CO)₂NO]⁺ (Cp = η⁵-C₅H₅, MeCp = η⁵-C₅H₄CH₃), [CpRe(CO)₂NO]⁺, [CpMn(CO)(L)NO]⁺ (L = PPh₃, PEt₂Ph, AsPh₃, CNMe, CNEt), {[CpMn(CO)NO]₂Me₂PC₂H₄PMe₂}²⁺ and {CpMn(CO)NO]₂Ph₂PC₂H₄PPh₂}²⁺ with liquid NH₃ yield the neutral carbamoyl complexes CpMn(CO)(NO)CONH₂, MeCpMn(CO)(NO)CONH₂, CpRe(CO)(NO)CONH₂, CpMn(L)(NO)CONH₂ (L = PPh₃, PEt₂Ph, AsPh₃, CNMe, CNEt), [CpMn(NO)CONH₂]₂Me₂PC₂H₄PMe₂ and [CpMn(NO)CONH₂]₂Ph₂PC₂H₄PPh₂. Properties and reactions of these new compounds are described.     

Zur Kristallchemie der Oxoplatinate

On the Crystal Chemistry of Oxoplatinates Referring to the coordination of Pt²⁺ and Pt⁴⁺ by oxygen the crystal structures of oxoplatinates will be systemized. Pt²⁺ exclusively shows in solids a square and planar coordination well known and typical for Cu²⁺, Pd²⁺ and Ni²⁺ too. Often mixed valences (Pt²⁺/Pt⁴⁺) are observed in square planar oxygen surrounding. Some exceptionally rare coordination is the dumbbell like O—Pt²⁺—O. The crystal chemistry of Pt⁴⁺ resembles the countless metal ions showing octahedral coordination by oxygen. Despite different compositions the compounds BaLn₂PtO₅, Ba₃Cu₂Ln₂PtO₁₀, Ba₅Ln₈Zn₄O₂₁, Ba₁₃Ln₈Zn₄Pt₄O₃₇ and Ba₁₇Ln₁₆Zn₈Pt₄O₅₇ show amazing relationships of polyhedra connections. Additionally will be shown that Ba₄Sm₄Zn₃PtO₁₅ is isotypic to Ba₆Nd₂Al₄O₁₅ and Ba₄NaCu_{0, 5}Pt_{1, 5}O₈ to Ba₁₅Pt₆O₂₇. Oxoplatinates containing lone pair active elements show one side open polyhedra. The positions of the free (s²) electrons are calculated using the Coulomb terms of lattice energy.     

Untersuchungen an Polyhalogeniden. XXIII. Kristallstrukturen der N-Alkylurotropiniumtriiodide UrRI3 mit R = Methyl,Ethyl, n-Propyl und n-Butyl

Studies on Polyhalides. 23. Crystal Structures of N-Alkylurotropinium Triiodides UrRI₃ with R = Methyl, Ethyl, n-Propyl, and n-Butyl The salts UrRI₃ may be prepared by the reaction of N-alkylurotropinium iodides UrRI with iodine I₂ at room temperature from aqueous solution. N-methylurotropinium triiodide C₇H₁₅N₄I₃ crystallizes monoclinically in P2₁/c with a = 1300.8(2) pm, b = 1276.0(3) pm, c = 859.3(2) pm, β = 94.75(2)° and Z = 4. The crystal structure is built up from layers of cations UrMe⁺ and of linear symmetric triiodide ions I₃^? alternating along [100]. N-ethylurotropinium triiodide C₈H₁₇N₄I₃ crystallizes orthorhombically in Pnma with a = 1397.3(5) pm, b = 1221.3(2) pm, c = 886.2(2) pm and Z = 4. The cationic (UrEt⁺) and anionic (I₃^?) layers alternate along [0 10]. N-propylurotropinium triiodide C₉H₁₉N₄I₃ crystallizes monoclinically in P2₁/c with a = 1885.7(5) pm, b = 1657.1(5) pm, c = 1700.5(4) pm, β = 112.39(2)° and Z = 12. The three independent cations and anions are slightly, but differently distorted. N-butylurotropinium triiodide C₁₀H₂₁N₄I₃ crystallizes monoclinically in P2₁/m with a = 991.8(3) pm, b = 757.8(2) pm, c = 1128.2(2) pm, β = 90.73(2)° and Z = 2. The crystal structure is stacked by alternating cationic and anionic layers along [001]. The triiodide ion is asymmetric and linear.     

Nitridsulfidchloride der Lanthanide: III. Synthese und Kristallstruktur von Pr5N3S2Cl2

Nitride Sulfide Chlorides of the Lanthanides. III. Synthesis and Crystal Structure of Pr₅N₃S₂Cl₂ By reacting praseodymium with sulfur, sodium azide and praseodymium trichloride in sealed, evacuated silica tubes (850°C, 7 d), the nitride sulfide chloride Pr₅N₃S₂Cl₂ is obtained in case of a 4:2:1:1 molar ratio of the reactants (Pr:S:NaN₃:PrCl₃). A slight excess of trichloride or the addition of NaCl as a flux supports the yield of brownish red, rod-shaped transparent crystals which prove to be stable against hydrolysis. The crystal structure (monoclinic, C2/m (no. 12), a = 1540.2(1), b = 400.92(3), c = 1656.3(1) pm, β = 101.24(1)°, Z = 4, R = 0.039, R_w = 0.028) was determined by means of X-ray single crystal data. Thus five crystallographically different cations (Pr³⁺) are present which with three distinct kinds of nitride anions (N^3?) build up two types of translationally commensurate chains from interconnected [NPr₄] tetrahedra. With an additional edge per “chain-link” in chain I, two single chains [NPr_3/3^ePr_1/1^t]³⁺ (?[NPr₂]³⁺) of cis-edge connected [NPr₄] tetrahedra (known from the Sm₄N₂S₃-type structure) are condensed into the double chain [(N1){(Pr1)_(2+2)/(2+2)^e,e(Pr2)_(2+1)/(2+1)^e,v}(N2)(Pr3)_1/1^t]³⁺ (?[N₂Pr₃]³⁺). Chain II consists of two single chains [NPr_2/2^vPr_2/1^t] ⁶⁺ (?[NPr₃]⁶⁺) of vertex-connected [NPr₄] tetrahedra (known from the Sm₃NS₃-type structure), which are condensed to the double chain [(N3)(Pr4)_2/2^e(Pr5)_2/2^v]³⁺ (?[NPr₂]³⁺) via an additional edge per “chain-link” too. Both types of chains are bundled along [010] like a closest packing of rods. Four crystallographically different but by X-ray diffraction indistinguishable anions S^2? and Cl^? hold both cationic double chains together and also adjust the charge balance in a molar ratio of 1 : 1.