ISSN:
0044-2313
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Sulfate, Phosphate, and Arsenate as Tridentate Ligands. Synthesis and Crystal Structures of (NMe4)2[Re3Cl9O3SO], (NMe4)2(H7O3)[Re3Cl9O3PO] and (NMe4)2(H5O2)[Re3Cl9ODark red (NMe4)2[Re3Cl9O3SO] (1) (monoclinic, P21/c, a = 1129.77(6) pm, b = 1890.46(7) pm, c = 1290.09(9) pm, β = 97.29(1)°, Vm = 411.49(4) cm3/mol) is obtained by direct reaction of rhenium trichloride with NMe4Cl in hydrochloric acid solution in the presence of sulfuric acid. Dark red crystals of (NMe4)2(H7O3)[Re3Cl9O3PO] (2) (monoclinic, P21/c, a = 1249.3(1) pm, b = 1760.5(2) pm, c = 1335.1(1) pm, β = 91.71(1)°, Vm = 441.91(7) cm3/mol) and (NMe4)2(H5O2)[Re3Cl9O 3AsO] (3) (monoclinic, P21/c, a = 975.23(6) pm, b = 1838.6(1) pm, c = 1572.31(7) pm, β = 92.39(1)°, Vm = 424.10(4) cm3/mol) grow from the hydrochloric acid solution of NMe4Cl of the violet precipitate that is obtained previously by the reaction of ReCl3 and Ag3[MO4] (M = P, As) in acetone solution. Important features of the crystal structures of (1), (2), and (3) are anionic building units [Re3Cl9O3MO]n- (M = S, n = 2; M = P, As, n = 3), where the tetrahedral anions [MO4]n- act as tridentate ligands. In the structures of (2) and (3) the anions form a hydrogen bonding system together with the cations H7O3+ (2) and “H5O2+” (3).
Notes:
Tiefrotes (NMe4)2[Re3Cl9O3SO] (1) (monoklin; P21/c: a = 1129,77(6) pm; b = 1890,46(7) pm; c = 1290,09(9) pm; β = 97,29(1)°; Vm = 411,49(4) cm3/mol) ist durch direkte Umsetzung von Rheniumtrichlorid mit NMe4Cl in salzsaurer Lösung in Gegenwart von Schwefelsäure zugänglich. Tiefrote Kristalle von (NMe4)2(H7O3)[Re3Cl9O3PO] (2) (monoklin; P21/c; a = 1249,3(1) pm; b = 1760,5(2) pm; c = 1335,1(1) pm; β = 91,71(1)°; Vm = 441, 91(7) cm3/mol) und (NMe4)2(H5O2)[Re3Cl9O 3AsO] (3) (monoklin; P21/c; a = 975,23(6) pm; b = 1838,6(1) pm; c = 1572,31(7) pm; β = 92,39(1)°; Vm = 424,10(4) cm3/mol) erhält man durch Umsetzung von ReCl3 mit Ag3[MO4] (M = P, As) in Aceton und anschließende Umsetzung des gebildeten violetten Niederschlags beim Eindunsten salzsaurer Lösungen in Gegenwart von NMe4Cl. Hervorstechende Strukturmerkmale von (1), (2) und (3) sind anionische Baugruppen [Re3Cl9O3MO]n- (M = S, n = 2; M = P, As, n = 3), in denen die tetraedrischen Anionen [MO4]n- als dreizähnige Liganden fungieren. In (2) und (3) sind die Anionen mit den Kationen H7O3+ (2) bzw. „H5O2+“ (3) in ein ausgedehntes System von Wasserstoffbrücken-Bindungen eingebunden. 3AsO].
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19905870121
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