Ligand substitution reactions chromium complexes

As already mentioned, complexes of chromium(iii), cobalt(iii), rhodium(iii) and iridium(iii) are particularly inert, with substitution reactions often taking many hours or days under relatively forcing conditions. The majority of kinetic studies on the reactions of transition-metal complexes have been performed on complexes of these metal ions. This is for two reasons. Firstly, the rates of reactions are comparable to those in organic chemistry, and the techniques which have been developed for the investigation of such reactions are readily available and appropriate. The time scales of minutes to days are compatible with relatively slow spectroscopic techniques. The second reason is associated with the kinetic inertness of the products. If the products are non-labile, valuable stereochemical information about the course of the substitution reaction may be obtained. Much is known about the stereochemistry of ligand substitution reactions of cobalt(iii) complexes, from which certain inferences about the nature of the intermediates or transition states involved may be drawn. This is also the case for substitution reactions of square-planar complexes of platinum(ii), where study has led to the development of rules to predict the stereochemical course of reactions at this centre. 

The reactivity of Cr complexes is marked by very slow Ligand Substitution reactions, resulting in unusual configurational stability. Many chiral complexes have been resolved. There has been a recent resurgence of interest in organochrominm(III) complexes, owing to the importance of chromium in catalytic processes see Chromium Organometallic Chemistry). 

Parsing for complex ions indicates that the solution will contain hexaaquairon(III) ion and hexaaquachromium(II) ion as complex ions, while the fluoride ion and water are possible ligands. The presence of a complex ion and a free ligand indicates that complex ion substitution reactions are possible. Since both chromium(II) ion and fluoride ion are hard, fluoride ion should substitute in a stepwise manner for the bound water molecules on the... 

The ligand substitution reactions of pentaaquachromium(III) alkyl complexes are unusually rapid compared to substitution on most chromium(III) complexes, and this is attributed to the trans-labilizing effect of the alkyl group/ Thus the substitution (41) falls into the SF time scale and is characterized by the rate constants in Table 9.8, and it is observed that relationship (42) holds for the... 

Two of the papers presented at the Fifth International Conference on Non-aqueous Solvents are of direct relevance to this Report. They deal with solvent effects on kinetics, in the areas of ligand substitution reactions at labile centres, and of preferential solvation in such systems." Another review on preferential solvation and its consequences deals primarily with chromium(iii) complexes, such as the [Cr(NCS)6] anion, in binary aqueous mixtures, but also mentions other groups of inorganic substrates such as low-spin iron(ii) complexes. A short article on the effectiveness of a solvent in catalysis considers such topics as affinities for nf-electrons and polarization potentials. ... 

Monstad, L. Monstad, G. Mechanism of Thermal and Photochemical Ligand Substitution Reactions of Chromium(III) and other Octahedral Metal Complexes, Coord. Chem. Revs. 1989,94,109-150. 

It will not have escaped the reader s attention that the kinetically inert complexes are those of (chromium(iii)) or low-spin d (cobalt(iii), rhodium(iii) or iridium(iii)). Attempts to rationalize this have been made in terms of ligand-field effects, as we now discuss. Note, however, that remarkably little is known about the nature of the transition state for most substitution reactions. Fortunately, the outcome of the approach we summarize is unchanged whether the mechanism is associative or dissociative. 

In order to gain more control over this reaction, chromium salphen dimers were synthesized. The synthetic route was developed in such a manner that the bridging length between the two salphen units can easily be varied and that the synthesis of heteronuclear metal complexes is possible. Since the ligand substitution pattern is highly important for the activity of the catalyst as well as the characteristics of produced polymer, an analogous monomeric Cr(lll) complex was synthesized for comparison [102] (Fig. 35). 

Aromatic ketones arylations, 10, 140 asymmetric hydrogenation, 10, 50 G—H bond alkylation, 10, 214 dialkylzinc additions, 9, 114-115 Aromatic ligands mercuration, 2, 430 in mercury 7t-complexes, 2, 449 /13-77-Aromatic nitriles, preparation, 6, 265 Aromatic nucleophilic substitution reactions, arene chromium tricarbonyls, 5, 234... 

To complete this treatment of the manifold types of reactions of the paramagnetic chromium complexes Cr(CO)jI and Cr2(CO)10I (cf. Section II1,D), it remains to discuss their behavior toward liquid NH3 (80). With CrfCOlgl, substitution of three CO ligands by NH3and addition of another NH3 molecule gives /rans-[Cr(CO)2(NH3)JI, which constitutes the first preparation of a cationic CO complex of chromium ... 

Photoreactions of [Cr(CO)3( /6-C7H8)] (41) with 6-mono- and 6,6-disub-stituted pentafulvenes (59a-59f) preferentially yield dicarbonyl complexes with substituted tj3 5-2-cyloheptadienylene-2-cyclopentadienylidenemethane chelate ligands (82,83). In the course of the reaction, C-6 of the fulvene forms a C—C bond to C-l of the 1,3,5-cycloheptatriene ligand, and one CO ligand is displaced. This reaction is of the same type as the formation of the f/3 5-[ 1 -(3-butene-1,2-diyl)-7-isopropylidenecycloheptadienyl] complexes 47c, 47e and 47t. The fulvene unit is transformed into a monosubstituted cyclo-pentadienyl entity, / -coordinated to the chromium, with the 1,3,5-cyclo-... 

Bis(benzene)chromium(0) is rather easily oxidized, but mixed complexes can be obtained by means of substitution reactions. For example, benzene will replace three CO ligands in chromium hexacarbonyl ... 

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