Chromium complex compounds, anions

Chromium (III) complex compounds, anions, oxalato, K3[Cr(C204)3]-3H20, 1 37... 

The Cr1 ion readily forms complexes it exists in aqueous solution as CrfH 0)j. and forms other complexes wilh anions, such asCr(H 0).CI , Crother properties due to variation in the bonding. Compounds or the trichloride have been reported with the following arrangements CrtHjOlsClj. [CrfHiOlsCljCIi- HiO. and [Cr(HiO)4Cf CU2 H 0 Trivalenl chromium also forms double salts, notably the chromium alums, hydrated double salts of Cr(III) sulfate and the alkali metal (or thallium or ammonium) sulfates. 

Reactions of metal carbonyls with Zintl phases do not always yield the desired result. An example is the reaction of KSi with the metal carbonyls M(CO)6 (M = Cr, Mo, W) and the chromium complex Cr(CO)sNMe3. Instead of forming a structure with a Si4 anion, KSi reduces these transition metal compounds to form the anions, [M2(CO)io] . In addition, certain organometallic transition metal clusters have been synthesized that contain Zintl anions coordinated to the metal, but Zintl compounds are not used as the reagents. 

Vanadium, the first element in Subgroup oA, and neighbour to chromium, is found in association with molybdenum in certain complex compounds. For example, when boiling solutions of molybdo-oxalates react with vanadium pentoxide, crystalline products are obtained which are thought to be substituted vanadates containing the complex anion... 

An example, developed by our group, has been presented 3-chloro-propenyl pivalate, the new synthon we propose as a formal a-hydroxy allyl anion, and chromium(II) chemistry allow to achieve the formal diastereo- and enantio-selective a-hydroxyallylation of carbonyl compounds by applying a catalytic cycle based on an in situ produced Salen-chromium complex (Table 8.3). 

It is well known that the tricarbonylchromium-complexed benzylic anions and cations are stabilized due to overlapping between d-orbital of the chromium and p-orbital of the benzylic carbon [1]. Tricarbonylchromium complexes of a-te-tralone and a-indanone having a carbonyl group at the side chain underwent a deprotonation of the exo-benzylic protons by treatment with base to give the stereo-controlled tricyclic compounds (Eqs. 1 and 2) [2]. In these cases, Robinson annulation products were formed in less than 10% yield. Also, base treatment of benzyl ether chromium complex having a chlorine at the side chain 3 gave cyclization product as a diastereomeric mixture (Eq. 3) [3]. 

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