ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Anionoidal Polyphosphanes as Chelate Ligands: Triphosphanato-P1,P3 Complexes of the Titanocene, Zirconocene, and hafnocene SystemMetallocene dichlorides (C5H5)2MCl2 (M = Ti, Zr, Hf; 1-3) react in dioxane/toluene or THF with dipotassium poly(organophosphanes) K2[PR]n to give, regardless of the chain length offered (n = 3 to 5) and of the organic substituent, the air-sensitive triphosphanato-P1, P3 chelates (C5H5)2M[PR]3, R being phenyl (1a-3b), ethyl (1b-3b), methyl (1c-3c) or tert-butyl (1d-3d). 31P NMR and mass spectra confirm the presence of four-membered MP3 rings. In accordance also with 1H NMR data, a structure model G of idealized Cs symmetry is proposed containing a folded chelate ring and an equatorial arrangement of the substituents r at the p atoms.
Notes:
Metallocen-dichloride (C5H5)2MCl2 (M = Ti, Zr, Hf; 1-3) reagieren in Dioxan/Toluol oder THF mit Dikalium-poly(organophosphanen) K2[PR]n unabhängig von der angebotenen Kettenlänge (n = 3-5) und vom Organosubstituenten zu luftempfindlichen Triphosphanato-P1, P3-Chelaten (C5H5)2M[PR]3 mit R = Phenyl (1a-3b), Ethyl (1b-3b), Methyl (1c-3c) oder tert-Butyl (1d-3d). 31P-NMR- und Massenspektren bestätigen das Vorliegen viergliedriger MP3 Ringe. Es wird ein Strukturmodell G idealisierter Cs-Symmetrie mit gefaltetem Chelatring und äquatorialen Substituenten R an den P-Atomen vorgeschlagen, das auch mit 1H—NMR-Daten in Einklang ist.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19811140807
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