Chromium complex, carbon monoxide

Catalysts which have been heated for one hour at 250°C. with carbon monoxide at 100 mm., cooled to 35°C., and pumped to remove physically adsorbed gas have far greater activities than untreated catalysts at all chromium concentrations (7). At low pressures, CO treatment increases the activity by at least an order of magnitude. As described in a previous publication, on the basis of infrared evidence, it is believed that the CO-treated catalyst is characterized by the presence of a carbon monoxide-chromium complex. 

CF3H, Methane, trifluoro-cadmium complex, 24 55 mercury complex, 24 52 CF3NOS, Imidosulfurous difluoride, (fluorocarbonyl)-, 24 10 CH2, Methylene ruthenium complex, 25 182 CH2CI4P2, Phosphine, methylenebis-(dichloro)-, 25 121 CH3, Methyl cobalt complexes, 23 170 mercury complexes, 24 143-145 platinum complex, 25 104, lOS CNO, Cyanato silicon complex, 24 99 CN2OS2, l,3k, 2,4-Dithiadiazol-5-one, 25 53 CO, Carbon monoxide chromium complexes, 21 1, 2 23 87 cobalt complex, 25 177 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

OC, Carbon monoxide chromium complex, 21 1, 2 chromium and tungsten complexes, 23 27 cobalt complex, 25 177 cobalt complexes, 23 15-17, 23-25 cobalt, iron, osmium, and ruthenium complexes, 21 58-65 cobalt-osmium complexes, 25 195-197 cobalt-ruthenium cluster complexes, 25 164... 

CH Methyl, cobalt complexes, 23 170 CO, Carbon monoxide, chromium complexes, 21 1, 2 23 87... 

OC, Carbon monoxide chromium complex, 21 1, 2 cobalt, iron, osmium, and... 

Chromium forms a white solid, hexacarhonyl, Cr(CO)j, with the chromium in formal oxidation state 0 the structure is octahedral, and if each CO molecule donates two electrons, the chromium attains the noble gas structure. Many complexes are known where one or more of the carbon monoxide ligands are replaced by other groups of ions, for example [CrfCOlsI] . 

A chromium atom forms a neutral complex with carbon monoxide molecules and 1,10-phenanthroline molecules. The structure of the complex is ... 

Low Oxidation State Chromium Compounds. Cr(0) compounds are TT-bonded complexes that require electron-rich donor species such as CO and C H to stabilize the low oxidation state. A direct synthesis of Cr(CO)g, from the metal and CO, is not possible. Normally, the preparation requires an anhydrous Cr(III) salt, a reducing agent, an arene compound, carbon monoxide that may or may not be under high pressure, and an inert atmosphere (see Carbonyls). 

If the reaction temperature is raised to 430 K and the carbon monoxide pressure to 3 atm, coordination of the metal atom in the rearranged product occurs via the phosphorus site, as in 159 (M = Cr, Mo, W) [84JOM(263)55]. Along with this product (M = W) at 420 K, formation of the dimer of 5-phenyl-3,4-dimethyl-2//-phosphole, 160 (the a complex), is possible as a consequence of [4 - - 2] cycloaddition reactions. Chromium hexacarbonyl in turn forms phospholido-bridged TiyP)-coordinatedcomplex 161. At 420 K in excess 2,3-dimethylbutadiene, a transformation 162 163 takes place (82JA4484). 

Aryl- and alkenylcarbene complexes are known to react with alkynes through a [3C+2S+1C0] cycloaddition reaction to produce benzannulated compounds. This reaction, known as the Dotz reaction , is widely reviewed in Chap. Chromium-Templated Benzannulation Reactions , p. 123 of this book. However, simple alkyl-substituted carbene complexes react with excess of an alkyne (or with diynes) to produce a different benzannulated product which incorporates in its structure two molecules of the alkyne, a carbon monoxide ligand and the carbene carbon [128]. As referred to before, this [2S+2SH-1C+1C0] cycloaddition reaction can be carried out with diyne derivatives, showing these reactions give better yields than the corresponding intermolecular version (Scheme 80). 

The thermal benzannulation of Group 6 carbene complexes with alkynes (the Dotz reaction) is highly developed and has been used extensively in synthesis [90,91]. It is thought to proceed through a chromium vinylketene intermediate generated by sequential insertion of the alkyne followed by carbon monoxide into the chromium-carbene-carbon double bond [92]. The realization that photodriven CO insertion into Z-dienylcarbene complexes should generate the same vinylketene intermediate led to the development of a photochemical variant of the Dotz reaction (Table 14). 

It is quite possible for a metal centre to possess a zero or negative oxidation state. Thus, the species [Cr(C0)6] and [Fe(C0)4] are chromium(O) and iron(-2) complexes. We will see in a later chapter that it is not a coincidence that these low formal oxidation states are associated with ligands such as carbon monoxide. 

Merlic demonstrated the direct, non-photochemical insertion of carbon monoxide from acylamino chromium carbene complexes 14 to afford a presumed chromium-complexed ketene 15 <00JA7398>. This presumed metal-complexed ketene leads to a munchnone 16 or munchnone complex which undergo dipolar cycloaddition with alkynes to yield the pyrroles 17 upon loss of carbon dioxide. 

The first metal-olefin complex was reported in 1827 by Zeise, but, until a few years ago, only palladium(II), platinum(Il), copper(I), silver(I), and mercury(II) were known to form such complexes (67, 188) and the nature of the bonding was not satisfactorily explained until 1951. However, recent work has shown that complexes of unsaturated hydrocarbons with metals of the vanadium, chromium, manganese, iron, and cobalt subgroups can be prepared when the metals are stabilized in a low-valent state by ligands such as carbon monoxide and the cyclopentadienyl anion. The wide variety of hydrocarbons which form complexes includes olefins, conjugated and nonconjugated polyolefins, cyclic polyolefins, and acetylenes. 

Chelating polyolefins displace carbon monoxide from chromium hexa-carhonyl to form stable olefin complexes. Thus cyclo-octa-1,5-diene gives the yellow complex [Cr(CO)4(C8H12)] for which the cfs-structure (VI M = Cr) is proposed (79). 

Tetracyclone reacts with chromium hexacarbonyl to give black, air-sensitive products which contain no carbon monoxide groups, and are probably analogous to the cobalt complex (XXV) (215). 

These reactions may proceed through an M(C5H6)2 intermediate, but in the absence of isolated or trapped intermediates there is no compelling evidence that this is so. Chromium vapor-C5H6 condensates liberate H2 only on warming, and, in this case, it has been possible to isolate a complex by trapping with carbon monoxide ... 

Mirkin and coworkers reported on catalytic molecular tweezers used in the asymmetric ring opening of cyclohexene oxide. In this case the early transition metal is the catalyst and rhodium functions as the structural inductor metal. The catalyst consists of two chromium salen complexes, the reaction is known to be bimetallic, and a switchable rhodium complex, using carbon monoxide as the switch. Indeed, when the salens are forced in dose proximity in the absence of CO the rate is twice as high and the effect is reversible [77]. 

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