Niobium complexes metals

The first complexes of a-keto ylides and group 5 early transition metals have only recently been obtained by reaction of Nb(III) derivatives [[NbCl3(dme) (R C=CR")] with 25 (R = thiazolyl) (Scheme 16). The chelation of the ylide occurs through an N,0-coordination to the metal center and in presence of MeLi a deprotonation of a phenyl ring takes place with the loss of alkyne, leading to the formation of a new orfho-metallated binuclear compound 32. The two ylides involved in the complexation behave as tridentate anionic ligands and are mutually in a trans disposition in order to minimize the steric hindrance [71,72]. Another binuclear niobium complex 33 has been obtained from 25 (R = Me, Ph) with this time an 0-coordinated a-keto ylide [68]. 

Acetyl ligands, in niobium complexes, C-H BDEs, 1, 298 Achiral phosphines, on polymer-supported peptides, 12, 698 Acid halides, indium compound reactions, 9, 683 Acidity, one-electron oxidized metal hydrides, 1, 294 Acid leaching, in organometallic stability studies, 12, 612 Acid-platinum rf-monoalkynes, interactions, 8, 641 Acrylate, polymerization with aluminum catalysts, 3, 280 Acrylic monomers, lanthanide-catalyzed polymerization,... 

Some complexes are known in which carbon dioxide is bonded to a transition metal. Aresia era/. [19) isolated the nickel complex (1)in which the CO ligand is coordinated througli the carbon atom and one of the oxygen atoms. Fachinetti et al. [20] found the polymeric cobalt complex (2), in which carbon dioxide is C bonded to cobalt and 0-bonded to two different potassium ions. Lappert isolated tlie remarkably stable niobium complex (3). which was the first authentic CO complex of an early d-block metal [21 j. 

A related reaction is shown for the molybdenum-niobium complex (equation 9). As described in a review by Horowitz and Shriver on bridging carbonyl ligands, this complex is a rare example of a structure containing terminal, bridging, and r-bridging CO ligands. All such complexes, of necessity, include metal-metal bonding. 

The unsubstituted para-t-butyl calixarenes themselves complex metals via their aryloxide groups. Since aryloxide complexes are frequently oligomeric, the simple calixarenes do not give monomeric complexes. Aryloxides are hard ligands, therefore they readily form complexes with oxo-philic hard metal ions such as alkali metals, early transition metals, lanthanides, and actinides. Complexation is often inferred because the calixarene acts as a carrier for the metal ion from an aqueous to an organic phase. With the /wa-/-butylcalix[ ]arenes in alkaline solution, a value of n = 6 gives the best carrier for lithium(I), sodium(I), and potassium(I), with a value of n 8 giving the best carrier for rubidium(I) and caesium(I).15,16 Titanium(IV) complexes have been characterized,17-19 as well as those of niobium(V) and tantalum(V).20-22 These complexes are classified as... 

Although many transition-metal derivatives react with cyclopropenes by ring opening (See Section 2.C. and ref 107 for examples), 1,2-dimclhylcyclopropene was regenerated from the complex 8 by reaction with triphenylphosphane or carbon disulfide, and a number of related nickel ° and niobium complexes of cyclopropenes which retain the three-membered ring have been reported. ... 

Niobium (Nb, at. mass 92.91) hydrolyses (in the absence of complexing anions) over the pH range 0-14. Polymerized forms of Nb(V) give pseudo-solutions or they separate as a white precipitate. When fused with NaOH, Nb20s forms the niobate, which is soluble in NaOH solutions. Niobium(V) forms stable fluoride, tartrate, oxalate, and peroxide complexes. The niobium complexes are more stable than the corresponding Ta complexes. A niobium chloride complex is formed in >5 M HCl solutions. Niobium(V) can be reduced to coloured species of Nb(III) and Nb(IV). In an acid medium, zinc metal reduces Nb(V), but not Ta(V). 

Doye s group [81] showed that a dinuclear titanium-sulfonamidate complex (Scheme 21), with a tetrahedral sulfur in the ligand backbone, can be used for intermo-lecular hydroaminoalkylation as well. This system gives mixtures of branched and linear products, although to date there has been no mechanistic rationale provided for the reduced regioselectivity of group 4 metal complexes in this transformation. There has been one report by Zi s group [44] that describes axially chiral bis(sulfonamidate) tantalum and niobium complexes for application as precatalysts for hydroamination and hydroaminoalkylation. Unfortunately, these complexes did not show any reactivity for either of these reactions. 

The first tris(arene) niobium complex, [Nb(l-4-jj -anthracene)3], prepared by the Na or K anthracene reduction of NbCl4(THF)2, undergoes facile anthracene displacement in the presence of CO to afford [K(18-crown-6)(THF)2][Nb(CO)6]. Reduction of TaCls by sodium naphthalene provides [Na(THF)][Ta(jj -naphthalene)3], the first homoleptic naphthalene complex of a third row transition metal. This complex reacts with CO and anthracene to give [Ta(CO)e] and [Ta(l-4-jj -anthracene)3], respectively. The latter product reacts with cyclooctatetraene (COT) to give [Ta(COT)3]-.==i= ... 

The niobium complex 562 is formed by successive treatment of CpNbCU with magnesium metal and phenylacetylene. The complex yields a mixture of 1,2,4-and 1,3,5-triphenylbenzene on standing (equation 58). The catalytic system CpNbCl4/Mg(0) mediates the reaction of the diyne 563 with hex-3-yne to give the benzene derivative 564. ... 

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... 

Hydroamination is an atom-economical process for the synthesis of industrially and pharmaceutically valuable amines. The hydroamination reaction has been studied intensively, including asymmetric reactions, and a variety of catalytic systems based on early and late transition metals as well as main-group metals have been developed." However, Group 5 metal-catalysed hydroaminations of alkenes had not been reported until Hultzsch s work in 2011. Hultzsch discovered that 3,3 -silylated binaphtho-late niobium complex 69 was an efficient catalyst for the enantioselective hydroaminoalkylation of iV-methyl amine derivatives 70 with simple alkenes 71, giving enantioselectivities up to 80% (Scheme 9.30). Enantiomerically pure (l )-binaphtholate niobium amido complex 69 was readily prepared at room temperature in 5 min via rapid amine elimination reactions between Nb(NMe2)5 and l,l-binaphthyl-2-ol possessing bullqr 3,3 -silyl substituents. Since the complex prepared in situ showed reactivity and selectivity identical... 

Niobium pentachloride-tetrachloride equilibrium 42 Niobium-alkali metal chloride complexes 1... 

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