Chromium complexes structures

UV irradiation. Indeed, thermal reaction of 1-phenyl-3,4-dimethylphosphole with (C5HloNH)Mo(CO)4 leads to 155 (M = Mo) and not to 154 (M = Mo, R = Ph). Complex 155 (M = Mo) converts into 154 (M = Mo, R = Ph) under UV irradiation. This route was confirmed by a photochemical reaction between 3,4-dimethyl-l-phenylphosphole and Mo(CO)6 when both 146 (M = Mo, R = Ph, R = R = H, R = R" = Me) and 155 (M = Mo) resulted (89IC4536). In excess phosphole, the product was 156. A similar chromium complex is known [82JCS(CC)667]. Complex 146 (M = Mo, R = Ph, r2 = R = H, R = R = Me) enters [4 -H 2] Diels-Alder cycloaddition with diphenylvinylphosphine to give 157. However, from the viewpoint of Woodward-Hoffmann rules and on the basis of the study of UV irradiation of 1,2,5-trimethylphosphole, it is highly probable that [2 - - 2] dimers are the initial products of dimerization, and [4 - - 2] dimers are the final results of thermally allowed intramolecular rearrangement of [2 - - 2] dimers. This hypothesis was confirmed by the data obtained from the reaction of 1-phenylphosphole with molybdenum hexacarbonyl under UV irradiation the head-to-tail structure of the complex 158. 

Since the paper by Pilling and Bedworth in 1923 much has been written about the mechanism and laws of growth of oxides on metals. These studies have greatly assisted the understanding of high-temperature oxidation, and the mathematical rate laws deduced in some cases make possible useful quantitative predictions. With alloy steels the oxide scales have a complex structure chromium steels owe much of their oxidation resistance to the presence of chromium oxide in the inner scale layer. Other elements can act in the same way, but it is their chromium content which in the main establishes the oxidation resistance of most heat-resisting steels. 

Fig. la. Structure of the complex bis( -butoxysilane-diyl)tetracarbonyliron(O) x HMPA 4. b. Molecular structure of the chromium complex bis( -butoxy-silanediyl)pentacarbonylchromium(O) x HMPA 9. c. Van der Waals surface of 9... 

Chromium, (ri6-benzene)tricarbonyl-stereochemistry nomenclature, 1,131 Chromium complexes, 3,699-948 acetylacetone complex formation, 2,386 exchange reactions, 2,380 amidines, 2,276 bridging ligands, 2,198 chelating ligands, 2,203 anionic oxo halides, 3,944 applications, 6,1014 azo dyes, 6,41 biological effects, 3,947 carbamic acid, 2,450 paddlewheel structure, 2, 451 carboxylic acids, 2,438 trinuclear, 2, 441 carcinogenicity, 3, 947 corroles, 2, 874 crystal structures, 3, 702 cyanides, 3, 703 1,4-diaza-1,3-butadiene, 2,209 1,3-diketones... 

The potential of Fischer carbene complexes in the construction of complex structures from simple starting materials is nicely reflected in the next example. Thus, the reaction of alkenylcarbene complexes of chromium and tungsten with cyclopentanone and cyclohexanone enamines allows the di-astereo- and enantioselective synthesis of functionalised bicyclo[3.2.1]octane and bicyclo[3.3.1]nonane derivatives [12] (Scheme 44). The mechanism of this transformation is initiated by a 1,4-addition of the C -enamine to the alkenylcarbene complex. Further 1,2-addition of the of the newly formed enamine to the carbene carbon leads to a metalate intermediate which can... 

Structural analogues of the /]4-vinylketene E were isolated by Wulff, Rudler and Moser [15]. The enaminoketene complex 11 was obtained from an intramolecular reaction of the chromium pentacarbonyl carbene complex 10. The silyl vinylketene 13 was isolated from the reaction of the methoxy(phenyl)-carbene chromium complex 1 and a silyl-substituted phenylacetylene 12, and -in contrast to alkene carbene complex 7 - gave the benzannulation product 14 after heating to 165 °C in acetonitrile (Scheme 6). The last step of the benzannulation reaction is the tautomerisation of the /]4-cyclohexadienone F to afford the phenol product G. The existence of such an intermediate and its capacity to undergo a subsequent step was validated by Wulff, who synthesised an... 

The curves of Figure 2.9 exhibit the complex structure of the surface film. With increasing depth there is a peak of iron in the oxidized state at approximately 0.3 nm, and a peak of chromium in the oxidized state at about 1 nm irrespective of immersion time. The maximum concentration of oxidized iron decreases and the maximum concentration of oxidized chromium increases with increasing immersion time. 

Rather complex structures are obtained by a novel chromium(O)-mediated three-component domino [6jt+2jt] cycloaddition described by Rigby and coworkers [315]. Irradiation of a mixture of the chromium complex 6/4-134 and the tethered diyne 6/4-135 with a Pyrex filter at 0 °C gave the polycyclic compounds 6/4-136 in medium to good yield (Scheme 6/4.34). 

Various chromium-complex dyes were prepared recently by reacting ammonium chromium sulphate with a series of chelatable o,o -dihydroxyazopyridone structures (Scheme 5.9). Elemental analyses corresponded to a 1 2 metal-dye ligand ratio (5.35). The... 

TLC has been applied for the purity control of the newly synthetized o,o -dihydrox-yazo dyes and their chromium complexes. The structures of 7-hydroxy-o,o -dihydrox-yazo dyes and their chromium complexes are listed in Fig. 3.14. TLC purity check of o,o -dihydroxyazo dyes and their chromium complexes was performed on silica layers using 5 per cent water/ethanol and 5 per cent water-dimethylsulphoxide as the mobile phase, respectively. The formula and Rp values of 7-hydroxy-o//-dihydroxyazo dyes and their chromium complexes are compiled in Table 3.10. The retention values indicated that the TLC technique applied is suitable for the purity control of the these new dye compounds [92],... 

Fig. 3.14. The structures of 7-hydroxy-o,o -dihydroxy azo dyes and their chromium complexes. Reprinted with permission from H. Kocaokutgen et al. [92].

Another cobalt derivative with CoN6 coordination is [Co(sep)]3+. This is the complex formed by Co(III) with the ligand 1,3,6,8, 10,13,l,6,19-octaazabicyclo[6.6.6]eicosane, which is related to the diamino-sarcophagine seen for the chromium complexes, and is called sepulcrand . Figure 90 shows the octahedral structure of this complex.135... 

It is also worthy to note that the pentacarbonyl-tungsten complex of the phosphirenylium cation (5) has been recently reported, but no X-ray structure has been obtained. B3LYP/6-311G(d) optimization of the presumed -Cr(CO)5 complex of 5 resulted in an 7 -form (Figure 1) when starting from the bound chromium complex. Such a structure is in complete accord with a delocalized electronic structure of the cation. 

Pair-of-dimer effects, chromium, 43 287-289 Palladium alkoxides, 26 316 7t-allylic complexes of, 4 114-118 [9JaneS, complexes, 35 27-30 112-16]aneS4 complexes, 35 53-54 [l5]aneS, complexes, 35 59 (l8)aneS4 complexes, 35 66-68 associative ligand substitutions, 34 248 bimetallic tetrazadiene complexes, 30 57 binary carbide not reported, 11 209 bridging triazenide complex, structure, 30 10 carbonyl clusters, 30 133 carboxylates... 

Wood, R. M., Aboud, K. A., Palenik, R. C., and Palenik, G. J. (2000). Bond valence sums in coordination chemistry. Calculation of the oxidation state of chromium complexes containing only Cr-O bonds and a redetermination of the crystal structure of potassium tetra(peroxo)chromate(V). Inorg. Chem. 

The magnetic method cannot be applied to tripositive chromium, the structures of the two extreme types having the same number of unpaired electrons and entering into resonance with each other. The chemical properties of the chromium complexes indicate that chromium, like the other iron-group elements, forms hyperligating bonds... 

---