Vanadium isolation

Only the surface layers of the catalyst soHd ate generaHy thought to participate in the reaction (125,133). This implies that while the bulk of the catalyst may have an oxidation state of 4+ under reactor conditions, the oxidation state of the surface vanadium may be very different. It has been postulated that both V" " and V " oxidation states exist on the surface of the catalyst, the latter arising from oxygen chemisorption (133). Phosphoms enrichment is also observed at the surface of the catalyst (125,126). The exact role of this excess surface phosphoms is not weH understood, but it may play a role in active site isolation and consequently, the oxidation state of the surface vanadium. 

Nitroxyl radicals of diarylamines can also be obtained on oxidation with hydrogen peroxide in the presence of vanadium ions. Resonance helps stabili2e these radicals. Eor example, the nitroxide from 4,4 -dimethoxydiphenylainine [63619-50-1] is stable for years, whereas the radical from the unsubstituted diphenylamine caimot be isolated. Substitution in the ortho and para positions also increases the stabiUties of these nitroxides by inhibiting coupling reactions at these sites. However, they are not as stable as the stericaHy hindered tetramethylpiperidyl radical. 

Vanadium was first discovered in 1801 by del Rio while he was examining a lead ore obtained from Zimapan, Mexico. The ore contained a new element and, because of the red color imparted to its salts on heating, it was named erythronium (redness). The identification of the element vanadium did not occur until 1830 when it was isolated from cast iron processed from an ore from mines near Taberg, Sweden. It was given the name vanadium after Vanadis, the Norse goddess of beauty. Shordy after this discovery, vanadium was shown to be identical to the erythronium that del Rio had found several years eadier. 

A. M. del Rio in 1801 claimed to have discovered the previously unknown element 23 in a sample of Mexican lead ore and, because of the red colour of the salts produced by acidification, he called it erythronium. Unfortunately he withdrew his claim when, 4 years later, it was (incorrectly) suggested by the Frenchman, H. V. Collett-Desotils, that the mineral was actually basic lead chromate. In 1830 the element was rediscovered by N. G. Sefstrom in some Swedish iron ore. Because of the richness and variety of colours found in its compounds he called it vanadium after Vanadis, the Scandinavian goddess of beauty. One year later F. Wohler established the identity of vanadium and erythro-nium. The metal itself was isolated in a reasonably pure form in 1867 by H. E. Roscoe who reduced the chloride with hydrogen, and he was... 

The cobalt complex is usually formed in a hot acetate-acetic acid medium. After the formation of the cobalt colour, hydrochloric acid or nitric acid is added to decompose the complexes of most of the other heavy metals present. Iron, copper, cerium(IV), chromium(III and VI), nickel, vanadyl vanadium, and copper interfere when present in appreciable quantities. Excess of the reagent minimises the interference of iron(II) iron(III) can be removed by diethyl ether extraction from a hydrochloric acid solution. Most of the interferences can be eliminated by treatment with potassium bromate, followed by the addition of an alkali fluoride. Cobalt may also be isolated by dithizone extraction from a basic medium after copper has been removed (if necessary) from acidic solution. An alumina column may also be used to adsorb the cobalt nitroso-R-chelate anion in the presence of perchloric acid, the other elements are eluted with warm 1M nitric acid, and finally the cobalt complex with 1M sulphuric acid, and the absorbance measured at 500 nm. 

The role of steric influences on the formation of various vanadium amidinate complexes in the oxidation states +2 and +3 has been studied in detail. The reaction of VCl2(TMEDA)2 and of VCl3(THF)3 with 2 equivalents of formamidinate salts afforded dimeric V2[HC(NCy)2l4 (cf. Section IV.E) with a very short V-V multiple bond and [ [HC(NCy)2 V(/i-Cl)l2 which is also dimeric (Scheme 107). The formation of V2[HC(NCy)2l4 was shown to proceed through the intermediate monomeric [HC(NCy)2l2V(TMEDA), which was isolated and fully characterized. The dinuclear structure was reversibly cleaved by treatment with pyridine forming the monomeric [HC(NCy)2l2V(py)2. ... 

Fig. 3. Frequencies of three representative vanadium atom absorptions in different open-chain C Hj,+8 matrices (where n = 1-10), compared to gas-phase and argon-isolated atomic vanadium (109).

Under similar reaction-conditions, the vanadium species V(N2)6 (139) has been isolated. In addition, a species V2(Na) (n probably = 12) was observed (139). The metal nuclearity was established by the standard, metal-concentration techniques. A comparison of the optical spectra of V(N2) and V(CO)e 128) suggested that these molecules have very similar, electronic properties, and the data clearly established that N2 is a strong, field ligand in its bonding properties. Interestingly, atomic V could be isolated in N2 matrices from 8- 12K co-... 

Recently, several papers have appeared that report the isolation of stable complexes of vanadium(IV) with dithiocarboxylato ligands (77, 80). Dithiocarboxylato salts (PhCS, P-CH3C6H4CS2,... 

NifM is required for maturation of VnfH, and NifS and U seem to be important for provision of sulfide and probably iron for the biosynthesis of the vanadium nitrogenase. The apo VFe protein has been isolated from an A. vinelandii strain deleted for nifKD and nifB (169). It was an hexamer that could be activated in vitro by the addi-... 

An Fe-only nitrogenase has also been isolated from a nifH mutant of Rhodospirillum rubrum and was characterized as an a2/82<% hex-amer containing only iron, no molybdenum or vanadium, with an o 2Fe4S4-containing Fe protein. A factor could be extracted from the FeFe protein into NMF that combined with apo-MoFe protein to form an active enzyme 193). 

A preparation of the third nitrogenase from A. vinelandii, isolated from a molybdenum-tolerant strain but lacking the structural genes for the molybdenum and vanadium nitrogenases, was discovered to contain FeMoco 194). The 8 subunit encoded by anfG was identified in this preparation, which contained 24 Fe atoms and 1 Mo atom per mol. EPR spectroscopy and extraction of the cofactor identified it as FeMoco. The hybrid enzyme could reduce N2 to ammonia and reduced acetylene to ethylene and ethane. The rate of formation of ethane was nonlinear and the ethane ethylene ratio was strongly dependent on the ratio of nitrogenase components. 

Hara 1, T Sakurai (1998) Isolation and characterization of vanadium bromoperoxidase from a marine macroalga iicHowia stolonifera. J Inorg Chem 72 23-28. 

Catalytic turn-over [59,60] in McMurry couplings [61], Nozaki-Hiyama reactions [62,63], and pinacol couplings [64,65] has been reported by Fiirst-ner and by Hirao by in situ silylation of titanium, chromium and vanadium oxo species with McaSiCl. In the epoxide-opening reactions, protonation can be employed for mediating catalytic turn-over instead of silylation because the intermediate radicals are stable toward protic conditions. The amount of Cp2TiCl needed for achieving isolated yields similar to the stoichiometric process can be reduced to 1-10 mol% by using 2,4,6-collidine hydrochloride or 2,6-lutidine hydrochloride as the acid and Zn or Mn dust as the reduc-tant (Scheme 9) [66,67]. 

The presence of zinc with bidentate nitrogen donor ligands in the formation of novel composite materials by hydrothermal reactions has been studied. A zinc-containing one-dimensional material, [Zn(phenanthroline)Mo04] was isolated from molybdate, and from vanadium oxide in the presence of zinc 2,2 -bipyridine [Zn(2,2,-bipyridine)2V40i2] was obtained.212,213... 

The first structurally characterized triarylzincate [Li(TMEDA)2][Zn 2,4,6-(Pr1)3G6H2 3] 59 was a byproduct of the lithiation of VC13(THF)3 with Li(2,4,6-(Pr1)3C6H2)3, in which the vanadium compound had been pre-reduced with metallic zinc.116 In the solid state, the compound consists of isolated, tetrahedrally coordinated lithium ions and trigonal-planar tris(tris(isopropyl)phenyl)zincate ions. The Zn-G bonds are equidistant (2.039(7) A), but the C-Zn-C bond angles are variable, ranging from 112.2(3)° to 125.4(3)°. 

Several anionic metal carbonyl hydrides stoichiometrically convert acyl chlorides to aldehydes. The anionic vanadium complex [Cp(CO)3VH] reacts quickly with acyl chlorides, converting them to aldehydes [44]. Although no further reduction of the aldehyde to alcohol was observed, the aldehydes reacted further under the reaction conditions in some cases, so a general procedure for isolation of the aldehydes was not developed. 

These data taken together suggest that vanadium is deposited on the catalyst in three successive forms. The initial vanadium which appears on the catalyst is primarily an isolated V02+ species, presumably associated with alumina defect sites. This is followed by the diamagnetic vanadium surface phase and finally by the vanadium sulfides. This progression is illustrated by the analysis of catalyst samples taken from different positions in a reactor which had been employed in a pilot-plant treatment of a petroleum residuum (Figure 4). Note that all of... 

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