Aryl chromium halide

Ziegler-Natta Catalysts (Heterogeneous). These systems consist of a combination of a transition metal compound from groups IV to VIII and an organometallic compound of a group I—III metal.23 The transition metal compound is called the catalyst and the organometallic compound the cocatalyst. Typically the catalyst is a halide or oxyhalide of titanium, chromium, vanadium, zirconium, or molybdenum. The cocatalyst is often an alkyl, aryl, or halide of aluminum, lithium, zinc, tin, cadmium, magnesium, or beryllium.24 One of the most important catalyst systems is the titanium trihalides or tetra-halides combined with a trialkylaluminum compound. 

The catalytic process is also achieved in the Pd(0)/Cr(II)-mediated coupling of organic halides with aldehydes (Scheme 33) [74], Oxidative addition of a vinyl or aryl halide to a Pd(0) species, followed by transmetallation with a chromium salt and subsequent addition of the resulting organo chromate to an aldehyde, leads to the alcohol 54. The presence of an oxophile [Li(I) salts or MesSiCl] allows the cleavage of the Cr(III) - 0 bond to liberate Cr(III), which is reduced to active Cr(II) on the electrode surface. 

Nozaki-Hiyama-Kishi (NHK) reactions215,216 are well known and often employed as a useful method for the synthesis of natural products by coupling of allyl, alkenyl, alkynyl, and aryl halides or triflates with aldehydes. The organochromium reagents are prepared from the corresponding halides or triflates and chromium(ll) chloride, and are employed in polar aprotic solvents (THF, DMF, DMSO, etc.). Subsequently, it was found that nickel salts exhibited a significant catalytic effect on the formation of the C-Cr bond217,218 (Equation (19)). 

Arene(tricarbonyl)chromium complexes, 19 Nickel boride, 197 to trans-alkenes Chromium(II) sulfate, 84 of anhydrides to lactones Tetrachlorotris[bis(l,4-diphenyl-phosphine)butane]diruthenium, 288 of aromatic rings Palladium catalysts, 230 Raney nickel, 265 Sodium borohydride-1,3-Dicyano-benzene, 279 of aryl halides to arenes Palladium on carbon, 230 of benzyl ethers to alcohols Palladium catalysts, 230 of carboxylic acids to aldehydes Vilsmeier reagent, 341 of epoxides to alcohols Samarium(II) iodide, 270 Sodium hydride-Sodium /-amyloxide-Nickel(II) chloride, 281 Sodium hydride-Sodium /-amyloxide-Zinc chloride, 281 of esters to alcohols Sodium borohydride, 278 of imines and related compounds Arene(tricarbonyl)chromium complexes, 19... 

The fixation of C02 into a three-membered ring has also been promoted, under relatively severe conditions, by other catalytic systems such as tetrapheny-lantimony halides (333 K, 5 MPa) [68e] or the p-methoxyphenol/DMAP system (DMAP = 4,6-(dimethylamino)pyridine 393 K, 3.6MPa, 48h) [68f] or, under much milder conditions, by alkali [68g-k] or tetralkylammonium halides [68j], or by (Salen)Cr(III)(DMAP) [681]. It is worth noting that, with 2-alkyl or 2-aryl substituted aziridines, alkali or tetralkylammonium halides catalyze the formation of the 4-substituted regioisomer as the main or unique product, whereas the chromium(III) catalyst promoted the preferential conversion to the 5-subshtuted regioisomer with high selectivity and yield. 

Dinuclear carbonyl complexes, with copper, 2, 187-188 Dinuclear chromium(III) complexes, with halides, alkyls, aryls, 5, 317... 

Aryl halides may also be reacted with thiolate anions under phase-transfer conditions via activation by formation of tricarbonyl chromium complexes (equation 32)279 280 or other similar arene complexes281,282. 

Aryl halides may be carbonylated using several different palladium complexes and several different hydrogen donors839,840,842,843. In most synthetically useful reactions the conditions are reasonably low pressure (up to 6 bar) and reasonably low temperatures (below 100 °C). Halobenzenes have also been successfully carbonylated at 30 bar using a carbon monoxide/hydrogen mixture in the presence of a palladium catalyst and triethy-lamine. In this case the halobenzene must first be complexed with chromium tricarbonyl844. 

This method applies to aryl, alkenyl, allyl and alkynyl halides as well as to alkenyl Inflates and exhibits the same selectivity profile as its stoichiometric precedent (Scheme 4). Moreover, it does not matter if the catalytic cycle is started at the Cr or Cr " stage as implied by Scheme 3. Therefore it is possible to substitute cheap and stable CrClj for the expensive and air-sensitive CrCf previously used for Nozaki reactions. In some cases other chromium templates such as [Cp2Cr or [CpCrCl2] can be employed, improving the total turnover number of this transformation even further [13, 14]. 

Since 1939 I have come into closer contact with the organometallic chemistry of transition metals than I did during my first attempts to arylate Fe(CN)g , My attention was attracted to the paper by Job and Cassal, who synthesized chromium, molybdenum, and tungsten carbonyls by a simultaneous reaction of the halides with carbon monoxide and Grignard compounds. 

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