Showing papers by "Bernt Krebs published in 1982"

Structure of the Octabismuth(2+) Cluster in Crystalline Bi8(AlCl4)2

Abstract: The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 1108. DOI:10.1002/anie.198211080

[Fe6S9(SCH2C6H5)2]4−: A Hexanuclear Iron-Sulfur Cluster Anion Containing the Square-Pyramidal [(μ4-S)Fe4] Unit†

Abstract: The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 489. DOI:10.1002/anie.198204890

Doubly Metalated Carbon by Metal-Induced Vinyl-Ethylidene Rearrangement†

Abstract: The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 506. DOI:10.1002/anie.198205060

Darstellung von trans-[Mo6Cl8]Cl4Br22−ausgehend von kristallisierten [Mo6Cl8]Cl4(H2O)2 und die Kristallstruktur von [(C6H5)4As]2[Mo6Cl8]Cl4Br2†

Abstract: Die Darstellung der in der Uberschrift genannten Verbindung gelingt, wenn das kristallisierte [(Mo6Cl8)Cl4(H2O)2], das die H2O-Molekeln in trans-Stellung enthalt, in Ethanol mit HBr + [(C6H5)4As]Br in heterogener Reaktion umgesetzt wird. Die rontgenographische Untersuchung bestatigt, das im Kristall das isolierte trans-Br-substituierte Clusteranion [(Mo6Cl8)Cl4Br2]2− vorliegt. In homogener Losung laft die Reaktion weiter zu Br-reicheren Produkten. [(C6H5)4As]2[(Mo6Cl8)Cl4Br2] kristallisiert in der triklinen Raumgruppe P¯1 mit a = 11,071(2), b = 11,418(2), c = 12,813(2) A, α = 116,10(2), β = 95,27(2) und γ = 94,41(2)° (−133°C). Die Kristallstruktur bei −133°C wurde aus Einkristalldiffraktometerdaten bestimmt (R1 = 0,026). Die [(Mo6Cl8)Cl4Br2]2−-Anionen sind im Kristall nicht vollstandig geordnet, sondern verteilen sich statistisch im Verhaltnis 11:5:4 auf die bei definiertem [Mo6Cl8]-Gerust moglichen drei Positionen mit trans-standiger Anordnung der Br-Liganden. Die Geruste der Anionen bestehen aus Mo6-Clustern mit (leicht verzerrter) oktaedrischer Anordnung der Metallatome (d(MoMo): 2,600(1) bis 2,614(1) A), die quadratischpyramidal von Halogenatomen koordiniert sind. Die Einzelheiten der Struktur werden im Vergleich mit analog gebauten [(Mo6X8)Y6]-Clustern (X, Y Cl, Br) diskutiert. Preparation of trans-[Mo6Cl8]Cl4Br22− Starting from Crystalline [Mo6Cl8]Cl4(H2O)2 and Crystal Structure of [(C6H5)4As]2[Mo6Cl8]Cl4Br2 The synthesis of the title compound is successful if the crystallized [(Mo6Cl8)Cl4(H2O)2] containing the H2O molecules in trans-position reacts with HBr + [(C6H5)4As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo6Cl8)Cl4Br2]2− in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C6H5)4As]2[(Mo6Cl8)Cl4Br2] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) A, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (−133°C). The crystal structure at −133°C was determined from single crystal X-ray diffraction data (R1 = 0.026). The [(Mo6Cl8)Cl4Br2]2−-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo6Cl8]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo6 cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(MoMo): 2.600(1) up to 2.614(1) A), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo6X8)Y4] cluster units (X, Y Cl, Br).

[Fe6S9(SCH2C6H5)2]4-: Ein sechskerniges Eisen-Schwefel-Clusteranion mit zentraler quadratisch-pyramidaler [(μ4-S)Fe4]-Einheit†

Abstract: Das vollstandige Manuskript dieser Zuschrift erscheint in: Angew. Chem. Suppl. 1982, 489. DOI: 10.1002/ange.198204890

Oxotrihalogenoselenate(IV): Darstellung, Struktur und Eigenschaften von P(C6H5)4SeOCl3, P(C6H5)4SeOBr3 und As(C6H5)4SeOBr3

Abstract: The novel oxotribromosolcnate(IV) SeOBr3- anion was prepared from the reaction of stoichiometric quantities of SeOBr2 and bromide in acetonitrile solution, and it was isolated as the tetraphenylphosphonium and -arsonium salts in crystalline form. For the synthesis of the analogous SeOCl3- as P(C6H5)4SeOCl3, SeCl4 was reacted in the presence of a small quantity of H2O with P(C6H5)4Cl in acetonitrile. Complete X-ray structural analyses of P(C6H5)4SeOCl3 (space group P1̄, a = 10.981(3), b = 11.0511(3), c = 10.358(3) Å, α = 73.77(2)°, β = 83.33(2)°, γ = 80.51(2)°, V = 1187.9(6) Å3) and of P(C6H5)4SeOBr3 (space group P 21/c, a = 11.719(4), b = 16.088(4), c = 13.124(4) Å, β = 94.72(3)°, V = 2400(1) Å3) show dimeric centrosymmetric Se2O2Cl62- and Se2O2Br62- anions being present in the solid. In the anions two square-pyramidal (Ψ-octahedral) SeOHal4 groups are connected through a common Hal-Hal edge. The axial oxygen ligands (So-O: 1.597(4) and 1.584(0) Å) cause a pronounced stereochemical trans-activation of the inert pairs at the Se atoms. As(C6H5)4SeOBr3 is isotypic with P(C6H5)4SeOCl3.

Isopoly- und Heteropoly-Thioanionen. Kristall- und Molekülstrukturen von (PPh4)2[(WS4)WS(WS4)],CS2[(WS4)WO(WS4)H2O]·2H2O und (AsPh4)2[(WS4)Ni(WS4)]/Isopoly- and Heteropoly-Thioanions. Crystal and Molecular Structures of (PPh4)2[(WS4)WS(WS4)], Cs2[(WS4)WO(WS4)H2O] · 2 H2O and (AsPh4)2[(WS4)Ni(WS4)]

Abstract: The crystal and molecular structures of (PPh4)2[(WS4)WS(WS4)] (1a) and CS2[(WS4)WO(WS4)H2O] · 2 H2O (2a), which contain the first reported isopoly-thioanion of a transition metal have been determined: 1a: (P1̅, a = 913.0(1), b = 1060.1(2), c = 1333.9(2) pm, α = 87.11(1), β = 85.18(1), γ = 83.07(1)°, V = 1277.6 · 106 pm3, Z = 1); 2a: (P21/n, a = 671.6(2), b = 2018.5(4), c = 714.4(2) pm, β = 101.42(2)°, V = 949,3 · 106 pm3, Z = 2) and compared with that of the trimetallic heteropoly-thioanion of (AsPh4)2[(WS4)Ni(WS4)] (3a). 3a: (P1̄, a = 1255.2(3), b = 1277.1(3), c = 939.0(2) pm, α = 113.19(2), β = 96.28(2), γ = 108.72(2)°, V = 1261.5 · 106 pm3, Z = 1). Though there are delocalized orbitals in the isopoly-thioanions they can be regarded as coordination compounds of WIVX2+ containing two WVIS42- ligands.

Substitutionsreaktionen an Tetraschwefeltetranitriddichlorid

Abstract: Durch Reaktion von S4N4Cl2 (1) mit trimethylsilyl-substituierten Sulfodiimiden im Molverhaltnis 1:1 erhielten wir Derivate des Pentaschwefelhexanitrids 2a und b. Die Struktur von 2a wurde anhand einer Einkristallrontgenstrukturanalyse aufgeklart. 1 reagiert mit trimethylsilyl-substituierten Aminen zu den 1,5-Bis(amino)tetraschwefeltetranitriden 3a–c. Die unterschiedliche Orientierung der Substituenten konnte durch temperaturabhangige 1H-NMR-Untersuchungen belegt werden. In 2 und 3 bleibt die Kafigstruktur des freien S4N4 erhalten. Substitution Reactions at Tetrasulfur Tetranitridedichloride The reaction of S4N4Cl2 (1) with trimethylsilyl-substituted sulfodiimides in the molar ratio 1:1 leads to derivatives of pentasulfur hexanitride 2a and b. The structure of 2a was established by single X-ray crystal analysis. 1 reacts with trimethylsilyl-substituted amines to yield 1,5-bis(amino)-tetrasulfur tetranitrides 3a–c. The different orientation of the substituents was established by temperature-dependent 1H NMR investigations. In 2 and 3 the cage structure of the unsubstituted S4N4 is preserved.

Phosphazenes of coordination number 2 and 3. part 22. synthesis, molecular structure and ring opening of 1,2,3λ3‐diazaphosphiridins

Abstract: In einer Eintopfreaktion werden durch Metallierung des Di-tert.-butylhydrazins (I) und anschliesende Reaktion mit den Aminodifluorophosphinen (II) die 3′ P- und 13C-NMR-spektroskopisch charakterisierten Fluorophosphine (III) zuganglich und durch "HF"-Eliminierung mit Methyl-Li in die bei Raumtemp. uberraschend bestandigen Titelverbindungen (IV) umgewandelt.