ISSN:
0044-2313
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Complex Chemistry of Reactive Organic Compounds. XLV. Organometallic Methanediazo Complexes: Protonation and CycloadditionThe reactions of the methanediazo tungsten complex (η5-C5H5)W(CO)2(N2CH3) (1) with protic acids are strongly governed by solvent effects: while trifluoromethylsulfonic acid induces clean protonation with formation of the ionic derivative [(η5-C5H5)W(CO)2(HN2CH3)]+CF3SO3- (3) when diethylether is used as a solvent, compound 4 is formed in the presence of acetonitril which latter solvent has good coordination capabilities itself. Compound 4 originates from a novel type of cycloaddition reaction in which the protonated species of composition [(η5-C5H5)W(CO)(CH3CN)(HN2-CH3)]+CF3SO3- is involved. Complete elimination of the nitrogeneous ligand ensemble with concomitant formation of the halogen complex (η5-C5H5)W(CO)2Br3 (5) occurs upon treatment of 1 with hydrogen bromide.
Notes:
Stark ausgeprägte Solvens-Effekte beeinflussen die Säure-Reaktionen des Methandiazo-Wolfram-Komplexes (η5-C5H5)W(CO)2(N2CH3) (1): Während Trifluormethansulfonsäure in Diethylether die glatte Protonierung zum salzartigen Derivat [(η5-C5H5)W(CO)2(HN2CH3)]+CF3SO3- (3) bewirkt, bildet sich im koordinationsfähigen Lösungsmittel Acetonitril die Verbindung 4, die durch eine neuartige Cycloaddition eines Solvens-Moleküls an die protonierte Spezies [(η5-C5H5)-W(CO)(CH3CN)(HN2CH3)]+CF3SO3- zustandekommt. Mit Bromwasserstoff erfolgt vollständige Abspaltung des stickstoffhaltigen Ligandensembles zum Halogeno-Komplex (η5-C5H5)W(CO)2Br3 (5).
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19845080115
