ISSN:
0044-2313
Keywords:
Tetrabromobispyridinemolybdates
;
preparation
;
isomerisation
;
crystal structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Darstellung von cis-tetrabromobispyridinemolybdaten(III) und die Kristallstruktur von cis-(NH4)[MoBr4py2] · ⅓ H2O (py = Pyridin)(NH4)2[MoBr5 · H2O] reagiert mit Pyridin im Acetonitril (CH3CN) bei Zimmertemperatur. Das Produkt ist ein Gemenge von cis- und trans-(pyH)[MoBr4py2], das auf Grund der Löslichkeitsunterschiede aufgetrennt werden kann. cis-M[MoBr4py2] · ⅓ H2O (M = NH4+, Rb+, Cs+), cis-(bipyH)[MoBr4py2] (bipy = 2,2′-Bipyridyl) und cis-(PPh4)[MoBr4py2] wurden aus cis-(pyH)[MoBr4py2] dargestellt.In siedendem Acetonitril (82°C) erfolgt irreversible cis-trans-Isomerisierung. Brom oxidiert das cis-Diastereoisomere zu trans-MoBr4py2.Die Verbindungen wurden durch chemische Analyse, Infrarot-, UV-VIS-Spektroskopie, Konduktometrie und Röntgen-Pulveraufnahmen charakterisiert.Die Kristallstruktur von cis-(NH4)[MoBr4py2] · ⅓ H2O wurde bestimmt: rhomboedrisch, R3c, (No. 161), a = 15,809(3) Å, β = 112,79(2)°, Z = 6, Dröntg. = 2,29, Dgemess. = 2,27(3) g/cm3, V = 2 601(1) Å3, R1 = 0,046, Rw = 0,068. Die mittleren Mo—Br und Mo—N(Pyridin)-Abstände sind 2,58(2) bzw. 2,20(2) Å. cis-Rb[MoBr4py2] · ⅓ H2O und cis-Cs[MoBr4py2] · ⅓ H2O sind isostrukturell mit cis-(NH4)[MoBr4py2] · ⅓ H2O.
Notes:
The reaction between (NH4)[MoBr5 · H2O] and pyridine in acetonitrile (CH3CN) at room temperature results in the mixture of cis- and trans-(pyH)[MoBr4py2] which can be separated on the basis of solubility. cis-M[MoBr4py2] · ⅓ H2O (M = NH4+, Rb+, Cs+), cis-(bipyH)[MoBr4py2] (bipy = 2,2′-bipyridil) and cis-(PPh4)[MoBr4py2], were prepared from cis-(pyH)[MoBr4py2].At the temperature of boiling acetonitrile irreversible cis to trans isomerisation takes place. Bromine oxydizes cis isomers at room temperature to trans-MoBr4py2.The compounds were characterised by chemical analysis, infrared, UV-VIS spectroscopy, conductivity measurements and powder diffraction.The crystal structure of cis-(NH4)[MoBr4py2] · ⅓ H2O has been determined: rhombohedral, R3c, (No. 161), a = 15.809(3) Å, β = 112.79(2)°, Z = 6, DC = 2.29, DO = 2.27(3) g/cm3, V = 2 601(1) Å3, R1 = 0.046, Rw = 0.068. Average Mo—Br and Mo—N(pyridine) distances within the anion are 2.58(2) and 2.20(2) Å. cis-Rb[MoBr4py2] · ⅓ H2O and cis-Cs[MoBr4py2] · ⅓ H2O are isostructural with cis-(NH4)[MoBr4py2] · ⅓ H2O.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19946200534
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