Group vanadium complexes

Halides (chloride, in particular) also react promptly with surface OH groups, as has been shown for [W(=CCMe3)Cl3(dme)] and several inorganic oxides (silica, alumina, silica-alumina, niobia) [5-7]. The same was observed for the reaction of [V(=0)Cl3] with silica in this case, using a large excess of the vanadium complex, one mole of HCl is released per mole of grafted vanadium [8]. 

There are also several situations where the metal can act as both a homolytic and heterolytic catalyst. For example, vanadium complexes catalyze the epoxidation of allylic alcohols by alkyl hydroperoxides stereoselectively,57 and they involve vanadium(V) alkyl peroxides as reactive intermediates. However, vanadium(V)-alkyl peroxide complexes such as (dipic)VO(OOR)L, having no available coordination site for the complexation of alkenes to occur, react homolyti-cally.46 On the other hand, Group VIII dioxygen complexes generally oxidize alkenes homolytically under forced conditions, while some rhodium-dioxygen complexes oxidize terminal alkenes to methyl ketones at room temperature. 

Asphaltenes may contain both porphyrin and nonporphyrin metals, depending upon the origin of the crude oil. Yen et al. (1969) characterized the vanadium complexes in a petroleum asphaltene by mass spectroscopy, optical spectroscopy, and ESR. Porphyrins (Etio and DPEP), acid-resistant porphyrin macrocycles of increased aromaticity (Rhodo), and nonporphyrins with mixed donor complexes were identified. Baker (1966) and Baker et al. (1967) extracted porphyrins from Boscan crude oil asphaltenes and also found Etio and DPEP as the two major porphyrin series. These homologous series range in molecular weight by 7 to 18 methylene groups. Gallegos (1967) observed by mass spectroscopy that asphaltenes and maltenes from a Boscan crude oil had nearly identical porphyrins in terms of mass distribution. 

If the OH group is not blocked at all but left free, and the epoxidation reagent is the vanadium complex VO(acac)2 combined with f-BuOOH, the syn epoxide is formed instead. The vanadyl group chelates reagent and alcohol and delivers the reactive oxygen atom to the same face of the alkene. 

Group 5 complexes tend to be less active in alkene polymerizations, although vanadium-based Ziegler catalysts have long been known. The compounds Cp Nb(i74-diene)X2 (X = CH3 or Cl), activated by MAO, catalyze the living polymerization of ethylene at -20°C.117... 

Compared with metal enolates, there have been very few reports on the direct structural analysis and theoretical studies of ynolates. An X-ray crystal structure of a vanadium complex of lithium ynolate with a porphyrinogen ligand (56) is reported. This metal complex was incidentally formed from VCl3(THF)3 with tetralithium salt of the octaethyl-porphyrinogen ligand. In this complex, the lithium cation seems to interact with the 7T-electrons of the ynolate. The four atoms of the ynolate group in 56 are not collinear due to a partial sp character of the group in this complex. 

Labeling studies have clearly shown that the active catalyst is not a peroxo compound but an alkyl peroxide in which the alkyl peroxide group is probably 0,0-triangularly bonded to the metal,as illustrated by the X-ray crystal structure of the vanadium complex (22). The well-characterized d" metal 0,N-bonded N,JV-dialkylhydroxylamino complexes (79), (80) and (81) might be reminiscent of the alkyl peroxide complexes of Mo " , V " and Ti ", which are difiBcult to isolate and involved as reactive intermediates in reactions (64) or (65). 

The solid-state and solution chemistry of triethanolamine complexes has been investigated. While the solid-state structure was maintained in organic solvent (38), a different structure was observed in aqueous solution.262 170 NMR spectroscopy was used to demonstrate that the two oxo groups were different and in combination with H and 13C NMR data, defined the structure as (39).262 Speciation studies and a detailed characterization of this class of compounds were important because the ligand is a commonly used buffer in biology and the complexes are model systems for interactions with proteins.61,263 The thermodynamic parameters were determined for several derivatized diethanolamine ligand-vanadium(V) complexes, and represent some of the few vanadium complexes for which such parameters are known.62 The structure of (nitrilotriacetato)dioxovanadate was reinvestigated.2 4... 

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