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  • Articles: DFG German National Licenses  (5)
  • 1990-1994  (5)
  • crystal structure  (4)
  • 1,2,3-Diazaphospholes  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 411-414 
    ISSN: 0009-2940
    Keywords: Phosphaalkyne, amino- ; [3 + 2] Cycloaddition ; 1,2,4-Diazaphospholes ; 1,2,3-Diazaphospholes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactive E = C(p - p)π Systems, XXXII[1].  -  First Representatives of Amino-Substituted 1,2,4-Diazaphospholes(Diisopropylamino)phosphaethyne iPr2N - C≡P reacts at 20° C in a [3 + 2] cycloaddition with (trifluoromethyl)diazomethane (2a) or methyl diazoacetate (2b) to yield a mixture of the corresponding regioisomers 1H-1,2,4-diazaphospholes (5a or 5b) and 1H-1,2,3-diazaphospholes (6a or 6b) in quantitative yields (isomer ratio: 5a/6a = 2:1; 5b/6b = 4:1). X-ray diffraction studies on 5a and 5b indicate a delicate charge balance in the bonding system of 1H-1,2,4,σ2-diazaphospholes under the influence of the exocyclic push/pull substituents iPr2N and CF3 or CO2Me, respectively.
    Additional Material: 2 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: Selenium ; bromoselenates(II) ; preparation ; crystal structure ; FIR spectra ; Raman spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Structure, and Properties of the Novel Bromoselenates(II) [Se3Br8]2-, [Se4Br14]2-, and [Se5Br12]2-. Crystal Structures of [Cu(i-PropCN)4]2[Se3Br8], [EtPh3P]2[Se4Br14], and [n-Prop4N]2[Se5Br12]Using the symproportionation of elemental selenium and selenium tetrabromide in polar aprotic solvents a new class of tri-, tetra-, and pentanuclear bromoselenates(II) was obtained. In 2-methylpropionitrile solution the novel ion [Se3Br8]2- was stabilized and isolated as its black solvated copper salt. The crystals of [Cu(i-PropCN)4]2[Se3Br8] are monoclinic (C 2/c, a = 20.753(6), b = 13.344(4), c = 19.149(6) Å, β = 90.09(3)° at 140K, Z = 4) and contain trigonal star-shaped ions [Se3Br8]2- consisting of three edge-sharing square planar SeBr4 units. The mean terminal and μ3-bridging Se—Br bond lengths are 2.408 Å, respectively. [EtPh3P]2[Se4Br14] was obtained from dichloromethane solutions as dark red square-shaped crystals. The X-ray structure analysis (space group P 21/n, a = 11.400(3), b = 11.815(3), c = 20.720(A) Å, β = 92.50(3)° at 140 K, Z = 2) shows the crystals to contain tetranuclear ions [Se4Br14]2- that are built of two parallel planar [Se2Br6] units connected via two linear μBr-bridges. In the interesting delocalized electronic system a formal oxidation number of +1 has to be assigned to the bridging bromine. The mean terminal Se—Br bond length is 2.411 Å, the bridging bond lengths are 2.764 Å in the planar Se2Br6 units 2.594 Å in the linear Se—Br—Se bridges. Dark red [n-Prop4N]2[Se5Br12] was also isolated from CH2Cl2 solutions. It crystallizes in the tetragonal space group P 42/mnm (a = 14.798(3), c = 11.69(2) Å at 140 K, Z = 2) and its structure shows the novel pentanuclear ion [se5Br12]2-, consisting of a central square planar SeBr4 unit with two of its trans-edges being shared with additional pairs of square planar SeBr4, units. The anion can be described as two star-like Se3Br8 fragments with one sharing Se. The mean terminal and μ3-bridging Se—Br bond lengths are 2.343 Å and 2.956 Å, respectively. The vibrational spectra of the novel anions are reported and discussed.
    Notes: Durch Symproportionierung von elementarem Selen und Selentetrabromid in polaren protischen Lösungsmitteln wurde eine neue Klasse tri-, tetra- und pentanuklearer Bromoselenate(II) dargestellt. In 2-Methylpropionitril als Lösungsmittel wurde das strukturell neuartige Ion [Se3Br8]2- stabilisiert und als schwarzes solvatisiertes Kupfersalz isoliert. Kristalle von [Cu(i-PropCN)4]2[Se3Br8] sind monoklin (C2/c, a = 20,753(6), b = 13,344(4), c = 19,149(6) Å, β = 90,09(3)° bei 140K, Z = 4) und enthalten trigonale sternförmige Ionen [Se3Br8]2-, die aus drei kantenverknüpften quadratisch-planaren SeBr4-Einheiten bestehen. Die mittleren endständigen und μ3-verbrückenden Se—Br-Bindungslängen betragen 2,408 Å und 2,911 Å. [EtPh3P]2[Se4Br14] wurde aus Lösungen in Dichlormethan in Form dunkelroter Kristalle erhalten. Wie die Röntgenstrukturanalyse zeigt (Raumgruppe P21/n, a = 11,400(3), b = 11,815(3), c = 20,720(7) Å, β = 92,50(3)° bei 140K, Z = 2), enthalten sie vierkernige Ionen [Se4Br14]2-, die aus zwei parallel angeordneten, über lineare μBr-Brücken verknüpften Se2Br6-Einheiten aufgebaut sind. In diesem bemerkenswerten delokalisierten Elektronensystem muβ für das verbrückende Brom die formale Oxidationszahl + 1 angenommen werden. Die mittlere Se—Brterm-Bindungslängen sind 2,411 Å, die Brückenbindungslängen 2,764 Å in den planaren Se2Br6-Einheiten sowie 2,594 Å in den linearen Se—Br—Se-Brücken. Dunkelrotes [n-Prop4N]2[Se5Br12] konnte ebenfalls aus Lösungen in CH2Cl2 dargestellt werden. Es kristallisiert tetragonal (Raumgruppe P42/mnm, a = 14,798(3), c = 11,169(2) Å bei 140K, Z = 2). Seine Struktur enthält neuartige molekulare Ionen [Se5Br12]2-, die aus einer zentralen quadratisch-planaren SeBr4-Einheit bestehen, die über zwei trans-Kanten mit jeweils zwei weiteren quadratisch-planaren SeBr4-Einheiten verknüpft ist. Das Anion kann als über ein Selenatom verknüpfte Anordnung zweier sternförmiger Se3Br8-Fragmente beschrieben werden. Die mittleren endständigen und μ3-verbrückenden Se—Br-Abstände sind 2,343 Å und 2,956 Å. Über schwingungsspektroskopische Untersuchungen der neuen Anionen wird berichtet.
    Additional Material: 7 Ill.
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  • 3
    ISSN: 0044-2313
    Keywords: Aluminum sulfide ; crystal structure ; chemical transport ; five-coordinated aluminum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of a Novel Hexagonal Modification of Al2S3 with Five-coordinated AluminumA new hexagonal high temperature modification of Al2S3 could be prepared by chemical vapour transport with iodine (860 → 750°C) or by annealing of α -Al2S3 at 550°C. According to the single crystal X-ray structure determination the novel form of Al2S3 crystallizes in space group P 61 (No. 169) with a = 6.491(1), c = 17.169(4) Å, V = 626.5 Å3, Z = 6; R = 0.0253. In this modification one half of the aluminum atoms are tetrahedrally coordinated [d(Al—S): 2.226-2.267 Å], whereas the other half are in trigonal bipyramidal coordination of five S atoms with bond lengths of 2.272-2.315 Å (equatorial) and 2.495-2.521 Å (axial).Aluminum in AlS5 coordination is observed for the first time in this compound. The crystal structure is isotypic to In2Se3 and AlInS3. In addition, results of a refinement of the α -Al2S3 crystal structure are reported which were obtained on crystals prepared also by chemical vapour transport with iodine.
    Notes: Eine bisher noch nicht beschriebene hexagonale Hochtemperatur-Modifikation von Al2S3 konnte in reiner Form entweder durch chemischen Transport mit Iod (860 → 750°C) oder durch Tempern von α -Al2S3 oberhalb 550°C erhalten und durch eine Einkristall-Röntgenstrukturanalyse charakterisiert werden.Die neue Form des Al2S3 kristallisiert in der Raumgruppe P 61 (Nr. 169) mit a = 6,491(1), c = 17,169(4) Å, V = 626,5 Å3, Z = 6; R = 0,0253. In dieser Modifikation liegt die eine Hälfte der Aluminiumatome tetraedrisch koordiniert vor [d(Al—S): 2,226-2,267 Å], während die andere Hälfte trigonal-bipyramidal von fünf S-Atomen mit Al—S-Bindungslängen von 2,272 bis 2,315 Å (äquatorial) und 2,495-2,521 Å (axial) umgeben ist.Aluminium in AlS5-Koordination ist bisher unbekannt und wird hier zum ersten Mal beobachtet. Die Struktur ist isotyp zu In2Se3 und AlInS3. Zusätzlich wird über die Verfeinerung der Kristallstruktur α von -Al2S3 an Einkristallen berichtet, die ebenfalls durch chemischen Transport mit Iod hergestellt wurden.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0044-2313
    Keywords: Thio-chloro-indates ; thio-bromo-indates ; seleno-chloro-indates ; thio-chloro-gallates ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN and [Et4N]3[Ga3S3Cl6] · THF (X = Cl, Br; E = S, Se)[In2SCl6]2-, [In2SBr6]2-, [In3S3Cl6]3-, [In3Se3Cl6]3-, and [Ga3S3Cl6]3- were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph4P]2[In2SCl6] (1) (P1; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph4P]2[In2SBr6] (2) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX3, (CH3)3SiSSi(CH3)3 and Ph4PX (X = Cl, Br) in acetonitrile. The reaction of MCl3 (M = Ga, In) with Et4NSH/Et4NSeH in acetonitrile gave [Et4N]3[In3S3Cl6] · MeCN (3) (P21/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et4N]3[In3Se3Cl6] · MeCN (4) (P21/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et4N]3[Ga3S3Cl6] · THF (5) (P21/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In2SX6]2- anions (X = Cl, Br) in 1 and 2 consist of two InSX3 tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.
    Notes: [In2SCl6]2-, [In2SBr6]2-, [In3S3Cl6]3-, [In3Se3Cl6]3- und [Ga3S3Cl6]3- wurden als erste bisher bekannte Chalkogenohalogenoanionen von Elementen der 3. Hauptgruppe dargestellt. [Ph4P]2[In2SCl6] (1) (P1; a = 10,876(4) Å, b = 12,711(6) Å, c = 19,634(7) Å, α = 107,21(3)°, β = 96,80(3)°, γ = 109,78(3)°; Z = 2) und [Ph4P]2[In2SBr6] (2) (C2/c; a = 48,290(9) Å, b = 11,974(4) Å, c = 17,188(5) Å, β = 93,57(3)°, Z = 8) werden durch Reaktion von InX3, (CH3)3SiSSi(CH3)3 und Ph4PX (X = Cl, Br) in Acetonitril gebildet. [Et4N]3[In3S3Cl6] · MeCN (3) (P21/c; a = 17,328(4) Å, b = 12,694(3) Å, c = 21,409(4) Å, β = 112,18(1)°, Z = 4), [Et4N]3[In3Se3Cl6] · MeCN (4) (P21/c; a = 17,460(4) Å, b = 12,816(2) Å, c = 21,513(4) Å, β = 112,16(2)°, Z = 4) und [Et4N]3[Ga3S3Cl6] · THF (5) (P21/n; a = 11,967(3) Å, b = 23,404(9) Å, c = 16,260(3) Å, β = 90,75(2)°, Z = 4) können durch Umsetzung von MCl3 (M = Ga, In) mit Et4NSH (3), (5) bzw. Et4NSeH (4) in Acetonitril (3), (4) bzw. Tetrahydrofuran (5) erhalten werden. In den Kristallstrukturen der Titelverbindungen 1 bis 5 liegen isolierte Anionen und Kationen vor. Die [In2SCl6]2-- und [In2SBr6]2--Anionen in 1 und 2 lassen sich als Anordnung zweier über ein gemeinsames Schwefelatom eckenverknüpfter InSCl3- bzw. InSBr3- Tetraeder beschreiben. Die anionischen Teilstrukturen in 3, 4 und 5 werden durch drei Metallatome, die über μ2-E-Atome (E = Schwefel, Selen) zu einem Sechsring miteinander verbunden sind, aufgebaut, wobei zwei Chloratome an jedem Metallatom dessen verzerrt-tetraedrische Koordination vervollständigen.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 595 (1991), S. 167-182 
    ISSN: 0044-2313
    Keywords: Thallium(I) thiolates ; syntheses ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thallium(I) Thiolates: Synthesis, Structure, and Properties of TlSC6H5, TlS-t-C4H9, and TlSC7H7By reaction of thallium(I) salts with sodium thiolates in organic solvents it is possible to synthesize and crystallize polymeric and oligomeric neutral thallium(I) thiolate complexes. The polymeric crystal structure of yellow benzenethiolato thallium(I) TlSC6H5 (space group P213, a = 19.943(3) Å at 143 K) is built up by the two novel structure units [Tl7(SC6H5)6]+ and [Tl5(SC6H5)6]-. Yellow tert.-butanethiolato thallium(I) TlS-t-C4H9 (space group P1, a = 11.490(3), b = 11.490(3), c = 12.698(4) Å, α = 108.31(3), β = 91.21(2), σ = 116.99(3)° at 143 K) consists of [Tl8(S-t-C4H9)8] molecules, the thallium atoms being either in trigonal pyramidal or ψ-trigonal bipyramidal coordination. Yellow phenylmethanethiolato thallium(I) TlSC7H7 crystallizes as thin plates (space group: Pbcn, a = 31.215(9), b = 7.173(2), c = 7.184(2) Å at 293 K). The crystal structure contains chains of fourmembered Tl2S2 rings which are linked through trans edges to form a ladder-like arrangement. Each thallium atom is coordinated trigonal-pyramidally by three sulfur atoms. The vibrational spectra of the compounds are reported.
    Notes: Durch Umsetzung von Thallium(I)-Salzen mit Natriumthiolaten in organischen Lösungsmitteln gelang die Synthese und Kristallisation von polymeren und oligomeren neutralen TlI-Thiolat-Komplexen. Das gelbe Benzolthiolatothallium(I) TlSC6H5 (Raumgruppe P213, a = 19,943(3) Å bei 143 K) enthält in der polymeren Kristallstruktur die zwei neuartigen Strukturelemente [Tl7(SC6H5)6]+ und [Tl5(SC6H5)6]-. Die Thallium-Atome sind entweder trigonal-pyramidal oder ψ-trigonal-bipyramidal koordiniert. Das gelbe tert.-Butanthiolato-thallium(I) TlS-t-C4H9 (Raumgruppe P1, a = 11,490(3), b = 11,490(3), c = 12,698(4) Å, α = 108,31(3), β = 91,21(2), σ = 116,99(3)° bei 143 K) wird aus [Tl8(S-t-C4H9)8]-Molekülen aufgebaut, wobei die Thallium-Atome wieder trigonal-pyramidal und ψ-trigonal-bipyramidal koordiniert sind. Phenylmethanthiolato-thallium(I) TlSC7H7 kristallisiert in Form dünner gelber Plättchen (Raumgruppe: Pbcn, a = 31,215(9), b = 7,173(2), c = 7,184(2) Å bei 293 K). Die Kristallstruktur enthält Thallium-Thiolat-Ketten, die strickleiterartig aus trans-verknüpften Tl2S2-Vierringen bestehen. Jedes Thallium-Atom ist trigonal-pyramidal von drei Schwefel-Atomen koordiniert. Über schwingungsspektroskopische Untersuchungen wird berichtet.
    Additional Material: 7 Ill.
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