ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Arene(phosphane)metal Complexes, IV1). Synthesis of (6-Phosphonio-η5-cyclohexadienyl)ruthenium(II) Compounds and their Conversion into Dicationic (Benzene)ruthenium(II) Complexes[C6H6Ru(PR3)(PR3′)PR3″]2+The complexes [C6H6RuCl(PR3)PR3′]PF6 (1 - 4) and [C6H6RuCl2(PR3)] (9, 10) react with phosphanes PR3″ in the presence of NH4PF6 to give the (6-phosphonio-η5-cyclohexadienyl)ruthenium(II) compounds [(6-R3″P-η5-C6H6)Ru(PR3)(PR3′)PR3″](PF6)2 (5 - 8 11). Similarly, from [C6H6Ru(CH3CN)3](PF6)2 (12) and PMe3 the complex [(6-Me3P-η5-C6H6)Ru(PMe3)2CH3CN](PF6)2 (13) is formed. The IR and NMR spectra of 5 - 8, 11, and 13 indicate that the phosphonio group is in the exo-position at the sp3 carbon atom of the cyclohexadienyl ligand. Below - 30°C, rotation around the metal-ring bond is so hindered that rigid conformers are detected. Compounds 5 - 8 react with trifluoroacetic acid with elimination of the phosphonio group to yield the PF6 salts of the half-sandwich type complexes [C6H6Ru(PR3)(PR3′)PR3″]2+ (14 - 17).
Notes:
Die Komplexe [C6H6RuCl(PR3)PR3)]PF6 (1 - 4) und [C6H6RuCl2(PR3)] (9, 10) reagieren mit Phosphanen PR3″ in Gegenwart von NH4PF4 zu den (6-Phosphonio-η5-cyclohexadienyl)-ruthenium(II)-Verbindungen [(6-R3″P-η5-C6H6)Ru(PR3)(PR3″](PF6)2 (5 - 8, 11). Aus [C6H6Ru(CH3CN)3](PF6)2 (12) und PMe3 erhält man analog den Komplex (6-Me3P-η5-C6H6)Ru(PMe3)2CH3CN](PF6)2 (13). Die IR- und NMR-Spektren von 5 - 8, 11 und 13 weisen darauf hin, daß sich die Phosphoniogruppierung in der exo-Position am sp3-C-Atom des Cyclohexadienylliganden befindet. Unterhalb - 30°C ist die Rotation um die Metall-Ring-Bindung so stark behindert, daß starre Konformere nachweisbar sind. Die Verbindungen 5 - 8 reagieren mit Trifluoressigsäure unter Abspaltung der Phosphoniogruppe zu den PF6-Salzen der Halbsandwich-Komplexe [C6H6Ru(PR3)(PR3′)PR3″]2+ (14 - 17).
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19841170111
