ISSN:
0044-2313
Keywords:
Tetrafluoro-N-chloro-Imido Complexes of Molybdenum and Tungsten
;
Donor-Acceptor Complexes
;
Crystal Structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Reactions of MoNCl3 and WNCl3 with Elemental Fluorine. Crystal Structures of [MoO2F2(THF)2] and [WF4(NCl)(CH3CN)]The nitrido chlorides MoNCl3 and WNCl3 as well as WCl4(NCl) react with elemental fluorine forming the N-chloro imido complexes MoF4(NCl) and WF4(NCl), which were characterized by IR spectroscopy. With tetrahydrofurane MoF4(NCl) reacts to give [MoF4(NCl)(THF)], which in THF solution slowly converts into [MoO2F2(THF)2]. From WF4(NCl) with acetonitrile the complex [WF4(NCl)(CH3CN)] is obtained. Both donor acceptor complexes were characterized by crystal structure determinations.[MoO2F2(THF)2]: Space group P21/n, Z = 4, structure solution with 1823 unique reflections, R = 0.033 for reflections with I 〉 2σ(I). Lattice dimensions at -40°C: a = 636.2, b = 1119.5, c = 1625.2 pm; β = 93.92(1)º. The compound has a monomeric molecular structure with the fluorine atoms in trans-position to one another and with the oxygen atoms of the THF molecules in trans to the oxo ligands.[WF4(NCl)(CH3CN)]: Space group P21/m, Z = 2, structure solution with 1119 unique reflections, R = 0.038 for reflections with I 〉 2σ(I). Lattice dimensions at 20°C: a = 511.7, b = 714.9, c = 1002.5 pm; β = 102.59(10)º. The compound has a monomeric molecular structure in which the nitrogen atom of the acetonitrile molecule coordinates in trans-position to the N-chloro imido group W≡N—Cl. The structural parameters of this group are WN = 172.2 pm, NCl = 161.1 pm, WNCl = 178.6º.
Notes:
Die Nitridochloride MoNCl3 und WNCl3 reagieren ebenso wie WCl4(NCl) mit elementarem Fluor unter Bildung der N-chlorimido-Komplexe MoF4(NCl) und WF4(NCl), die durch ihre Spektren charakterisiert werden. Mit Tetrahydrofuran reagiert MoF4(NCl) unter Bildung von [MoF4(NCl)(THF)], das sich in THF-Lösung langsam in MoO2F2(THF)2 umwandelt. WF4(NCl) bildet mit Acetonitril den Komplex [WF4(NCl)(CH3CN)]. Von beiden Donor-Akzeptor-Komplexen wurden Kristallstrukturanalysen angefertigt.[MoO2F2(THF)2]: Raumgruppe P21/n, Z = 4, Strukturlösung mit 1823 unabhängigen Reflexen, R = 0,033 für Reflexe mit I 〉 2σ(I). Gitterkonstanten bei -40°C: a = 636,2; b = 1119,5; c = 1625,2 pm; β = 93,92(1)º. Die Verbindung hat eine monomere Molekülstruktur, in der die F-Atome in trans-Position zueinander und die O-Atome der THF-Moleküle in trans-Stellung zu den Oxoliganden angeordnet sind.[WF4(NCl)(CH3CN)]: Raumgruppe P21/m, Z = 2, Strukturlösung mit 1119 unabhängigen Reflexen, R = 0,038 für Reflexe mit I 〉 2σ(I). Gitterkonstanten bei 20°C: a = 511,7; b = 714,9; c = 1002,5 pm; β = 102,59(10)º. Die Verbindung hat eine monomere Molekülstruktur, in der das N-Atom des Acetonitrilmoleküls in trans-Stellung zur N-chlorimido-Gruppe W≡N—Cl angeordnet ist. Die Strukturparameter dieser Gruppe sind WN = 172,2 pm, NCl = 161,1 pm, WNCl 178,6º.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220715
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