ISSN:
0009-2940
Keywords:
Allyl compounds
;
Crotyl compounds
;
Vanadium chlorides, organo
;
Chromium chlorides, organo
;
Manganese chlorides, organo
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Alkylvanadium and Alkylniobium Reagents, III[1]. - Two Unconventional Chemical Methods for the Characterisation of Labile Transition Metal Complexes; Application to Allyl Derivatives of VIII, VV, CrIII, and MnIITwo little known chemical methods, the “Competition Constant Method” and the production of “Ligand Concentration/Product Yield Diagrams”, are suitable for the characterisation and identification of allyl and crotyl transition metal species prepared in solution. These methods (Figures 1 - 6) gave the following results: by transmetallation of 1 or 2 equivalents of allylMgBr with 1 equivalent of VCl3, CrCl3, or MnCl2 and subsequent reaction with ketones, a diallyl (2, 23, 25) and not a monoallyl derivative of the transition metal reacts with the ketones, suggesting that the equilibrium: 2 allylMCI (allyl)2M + MCl2 (M = VCl, CrCl, Mn) lies far to the right hand side. This assumption was confirmed by the IR spectrum in the case of vanadation of 1 and 2 equivalents of allylMgBr with VCl3 and corresponds with the observation that by chromation of allylMgBr with 1 equivalent of CrCl3 ca. 50% of the CrCl3 remain unaffected although the allylMgBr is completely consumed. Conversely, according to the results of the “Competition Constant Method” vanadation of 1, 2, or 3 equivalents of allylMgBr with VOCl3 gives three different allyl complexes which are believed to be allylVOCl2 (5), (allyl)2VOCl (6), and (allyl)3VO (7). Vanadation of 1 or 2 equivalents of crotylMgBr with 1 or 2 equivalents of VCl3 gives analogous results to the corresponding reactions with allylMgBr.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260920
Permalink
