Vanadium complexes arene

Snbsequent detailed kinetic stndies revealed that the reaction mechanism for the hydroxy-lation of arenes is mnch more complicated than that indicated above Furthermore, the active intermediate is likely an anion radical species formed upon interaction of two molecules of the vanadium peroxo complex. The sequence of the various steps is indicated in equations 17-24. The steps indicated in equations 17-21 refer to a radical chain which accounts for decomposition of the peroxo complex to form dioxygen, whereas the subsequent steps are those required for the functionalization of the substrate. 

C-M bond addition, for C-C bond formation, 10, 403-491 iridium additions, 10, 456 nickel additions, 10, 463 niobium additions, 10, 427 osmium additions, 10, 445 palladium additions, 10, 468 rhodium additions, 10, 455 ruthenium additions, 10, 444 Sc and Y additions, 10, 405 tantalum additions, 10, 429 titanium additions, 10, 421 vanadium additions, 10, 426 zirconium additions, 10, 424 Carbon-oxygen bond formation via alkyne hydration, 10, 678 for aryl and alkenyl ethers, 10, 650 via cobalt-mediated propargylic etherification, 10, 665 Cu-mediated, with borons, 9, 219 cycloetherification, 10, 673 etherification, 10, 669, 10, 685 via hydro- and alkylative alkoxylation, 10, 683 via inter- andd intramolecular hydroalkoxylation, 10, 672 via metal vinylidenes, 10, 676 via SnI and S Z processes, 10, 684 via transition metal rc-arene complexes, 10, 685 via transition metal-mediated etherification, overview,... 

Some examples of polynuclear polymeric metal arene complexes, obtained by cryosynthetic reactions from tin, titanium, vanadium, chromium, and molybdenum, are represented [202,542,543]. However, the preparative possibilities of such syntheses are not yet clear [201,202]. 

A variety of transition metals, for example, chromium, molybdenum, tungsten, iron, vanadium, manganese, and rhodium can be used to prepare relatively stable j -arene complexes (see Arene Complexes). Reactions of j -arene chromium tricarbonyl complexes have been extensively examined, and numerous reviews are available. Although chromium complexes are by far the most utilized in organic synthesis, complexes of iron and manganese are emerging as potentially useful alternatives. 

Several CT complexes of metal bis(arene) compounds containing, among others, the familiar organic acceptor TCNQ have been reported [71]. None of these materials has been shown to display physical properties superior to those of the metallocene systems. One very important exception is related to the reaction of bis(benzene) vanadium (which is isoelectronic with [MnCpf ]) with TCNE, which affords a material with unprecedented properties [72]. The amorphous material obtained displays bulk ferromagnetism at room temperature and its even exceeds the decomposition temperature of the sample of about 350 K. The compound is no longer an arene complex as it has an empirical composition corresponding to V(TCNE)2 1/2(CH2C12). 

In other systems, N—cleavage gives bis(/i-nitrido)dimetal diamond cores as the products of N2 cleavage. A reduced niobium complex of calix[4]arene reduces N2 in the presence of sodium metal, and a number of intermediates can be isolated. A related tridentate aryloxide ligand also splits N2 to give a diamond core with lithium ions bound to the nitrides. A vanadium diamidoamine complex reacts with N2 to give a product with a similar core structure, which may be further reduced by potassium graphite to a compound with one unpaired electron. This... 

The most general method for the preparation of carbonyl arene complexes is substitution of CO groups in metal carbonyls. Vanadium hexacarbonyl undergoes disproportionation in the presence of arenes ... 

Inter- and intramolecular (cyclometallation) reactions of this type have been ob-.served, for instance, with titanium [408,505,683-685], hafnium [411], tantalum [426,686,687], tungsten [418,542], and ruthenium complexes [688], Not only carbene complexes but also imido complexes L M=NR of, e.g., zirconium [689,690], vanadium [691], tantalum [692], or tungsten [693] undergo C-H insertion with unactivated alkanes and arenes. Some illustrative examples are sketched in Figure 3.37. No applications in organic synthesis have yet been found for these mechanistically interesting processes. 

Fewer electrochemical studies have been performed on low-oxidation-state complexes of vanadium, compared to higher oxidation states. Complexes in oxidation states lower than V(I) are limited to those which contain ligands such as strong 7T acids (CO and RNC), arenes, or tropy-lium. For example, the [Cp2Co][V(CO)6] salt contains V(-I) which undergoes a reversible oxidation at —0.54 V in CH2CI2 to form the 17-electron V(0) species [3]. 

Some work has been performed with bis (arene)vanadium and bis(heteroarene) vanadium complexes [7-10]. As indicated for the selected complexes shown in Table 1, replacement of benzene by phos-phabenzene and arsabenzene lowers the reduction potential. This counterintuitive result has been explained in terms of a greater positive charge on the metal... 

Tab. 1 Redox potentials of sonne bis(arene)vanadium complexes in DME versus SCE...

Arasabenzene, with chromium, 5, 339 Arcyriacyanin A, via Heck couplings, 11, 320 Arduengo-type carbenes with titanium(IV), 4, 366 with vanadium, 5, 10 (Arene(chromium carbonyls analytical applications, 5, 261 benzyl cation stabilization, 5, 245 biomedical applications, 5, 260 chiral, as asymmetric catalysis ligands, 5, 241 chromatographic separation, 5, 239 cine and tele nucleophilic substitutions, 5, 236 kinetic and mechanistic studies, 5, 257 liquid crystalline behaviour, 5, 262 lithiations and electrophile reactions, 5, 236 as main polymer chain unit, 5, 251 mass spectroscopic studies, 5, 256 miscellaneous compounds, 5, 258 NMR studies, 5, 255 palladium coupling, 5, 239 polymer-bound complexes, 5, 250 spectroscopic studies, 5, 256 X-ray data analysis, 5, 257... 

Bis( )6-arene)vanadium complexes applications, 5, 47 physical properties, 5, 47 reactivity, 5, 46 synthesis, 5, 45... 

Apart from the metal atom aggregation reactions described below, bis(arene)metal complexes of the early transition metals are resistant to ligand displacement The rings on the corresponding bis(naphthalene)metal species (41) are by, contrast, labile. Polymer-supported analogs of these naphthalene compounds with vanadium and chromium are known (42), but Ti atoms attack the polymer at the silicon ether linkage. These and other hybrid polymers can be further modified once the metal atom is incorporated. Thus a-methyl naphthalene is displaced from the hybrid organometallic polymer shown in Scheme 7 (43). 

The metal vapor ligand codeposition method has extended the array of such sandwich complexes. A wide range of substituents can be tolerated on the arene ring unusual arene M complexes have been prepared. Elschenbroichmade the interesting compound bis(j7 -phosphabenzene)vanadium, which is less air sensitive than the ligand itself. It turned out that the phosphorus heteroatom has a much stronger influence on the electron affinity of the free arene than of the bound arene. 

Another route to bis( -arene)vanadium(0) compounds is the cocondensation of arenes with vaporized vanadium metal (see Metal Vapor Synthesis of Transition Metal Compounds) On treatment with 1,3-cyclohexadiene and butyllithium, 15-electron vanadocene (5) is converted to 16-electron ( -benzene)( -cyclopentadienyl)vanadium(l) (6) (Scheme 3). Use of potassium naphthalenide affords the corresponding naphthalene complex. 

Vanadium hexacarbonyl reacts with various arenes yielding complexes [(arene)V(CO)4]" [V(CO)6] from which hexafluorphosphate or tetra-phenylborate salts can be prepared by metathesis reaction (50, 52). The cation [(CeHe)V(CO)4] reacts with NaBH4 to give the neutral cyclo-hexadienyl compound (CeH7)V(CO)4 (51). Similar results are observed with methyl-substituted derivatives. The addition of the hydride ion was shown to occur preferentially at unsubstituted positions of the aromatic ring. 

Finally, pentavalent vanadium complexes were employed as one-electron oxidants. The oxidative coupling of the electron-rich arene 48 in the presence of VOF3 was the key step in the total synthesis of stegnacin however, the cyclization to the... 

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