Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer (passivation) somewhat stabilizes the free metal against further oxidation.
The isolobal principle is a strategy used in organometallic chemistry to relate the structure of organic and inorganic molecular fragments in order to predict bonding properties of organometallic compounds. Roald Hoffmann described molecular fragments as isolobal "if the number, symmetry properties, approximate energy and shape of the frontier orbitals and the number of electrons in them are similar – not identical, but similar." One can predict the bonding and reactivity of a lesser-known species from that of a better-known species if the two molecular fragments have similar frontier orbitals, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Isolobal compounds are analogues to isoelectronic compounds that share the same number of valence electrons and structure. A graphic representation of isolobal structures, with the isolobal pairs connected through a double-headed arrow with half an orbital below, is found in Figure 1.
Cryptands are a family of synthetic bicyclic and polycyclic multidentate ligands for a variety of cations. The Nobel Prize for Chemistry in 1987 was given to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen for their efforts in discovering and determining uses of cryptands and crown ethers, thus launching the now flourishing field of supramolecular chemistry. The term cryptand implies that this ligand binds substrates in a crypt, interring the guest as in a burial. These molecules are three-dimensional analogues of crown ethers but are more selective and strong as complexes for the guest ions. The resulting complexes are lipophilic.
Salen refers to a tetradentate C2-symmetric ligand synthesized from salicylaldehyde (sal) and ethylenediamine (en). It may also refer to a class of compounds, which are structurally related to the classical salen ligand, primarily bis-Schiff bases. Salen ligands are notable for coordinating a wide range of different metals, which they can often stabilise in various oxidation states. These metal salen complexes primarily find use as catalysts.
In chemistry, a vanadate is a compound containing an oxoanion of vanadium generally in its highest oxidation state of +5. The simplest vanadate ion is the tetrahedral, orthovanadate, VO3−
4 anion, which is present in e.g. sodium orthovanadate and in solutions of V2O5 in strong base (pH > 13). Conventionally this ion is represented with a single double bond, however this is a resonance form as the ion is a regular tetrahedron with four equivalent oxygen atoms.
Palladium(II) cyanides are chemical species with the empirical formula Pd(CN)n(2-n)−. The dicyanide is a coordination polymer and was the first pure palladium compound isolated. In his attempts to produce pure platinum metal in 1804, W.H. Wollaston added mercuric cyanide to a solution of impure platinum metal in aqua regia. This precipitated palladium cyanide which was then ignited to recover palladium metal - a new element.
Vanadium trichloride is the inorganic compound with the formula VCl3. This purple salt is a common precursor to other vanadium(III) complexes.
Vanadyl(IV) sulfate describes a collection of inorganic compounds of vanadium with the formula, VOSO4(H2O)x where 0≤x≤6. The pentahydrate is common. This hygroscopic blue solid is one of the most common sources of vanadium in the laboratory, reflecting its high stability. It features the vanadyl ion, VO2+, which has been called the "most stable diatomic ion."
Vanadium hexacarbonyl is the inorganic compound with the formula V(CO)6. It is a blue-black volatile solid. This highly reactive species is noteworthy from theoretical perspectives as a rare isolable homoleptic metal carbonyl that is paramagnetic. Most species with the formula Mx(CO)y follow the 18-electron rule, whereas V(CO)6 has 17 valence electrons.
Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.
The vanadyl or oxovanadium(IV) cation, VO2+, is functional group that is common in the coordination chemistry of vanadium. Complexes containing this functional group are characteristically blue and paramagnetic. A triple bond is proposed to exist between the V4+ and O2- centers.
Tripodal ligands are tri- and tetradentate ligands with C3 symmetry. They are popular in research in the areas of coordination chemistry and homogeneous catalysis. Because the ligands are polydentate, they do not readily dissociate from the metal centre.
In organometallic chemistry, a transition metal indenyl complex is a coordination compound that contains one or more indenyl ligands. The indenyl ligand is formally the anion derived from deprotonation of indene. The η5-indenyl ligand is related to the η5cyclopentadienyl anion (Cp), thus indenyl analogues of many cyclopentadienyl complexes are known. Indenyl ligands lack the 5-fold symmetry of Cp, so they exhibit more complicated geometries. Furthermore, some indenyl complexes also exist with only η3-bonding mode. The η5- and η3-bonding modes sometimes interconvert.
Pentamethylcyclopentadienyl iridium dichloride is an organometallic compound with the formula [(C5(CH3)5IrCl2)]2, commonly abbreviated [Cp*IrCl2]2 This bright orange air-stable diamagnetic solid is a reagent in organometallic chemistry.
Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3COCHCOCH−
3) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR′−). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5H
7O−
2 in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).
Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2), often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer." It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).
UV is the +5 oxidation state of uranium which is found in the form of [UO2]1+. This species is known as pentavalent uranyl cation and has a low stability due to the disproportionation into tetravalent and hexavalent uranium species.
2UV → UIV + UVI
Vanadium phosphates are inorganic compounds with the formula VOxPO4 as well related hydrates with the formula VOxPO4(H2O)n. Some of these compounds are used commercially as catalysts for oxidation reactions.
Tetradentate ligands are ligands that bind with four donor atoms to a central atom to form a coordination complex. This number of donor atoms that bind is called denticity and is a way to classify ligands. Tetradentate ligands are common in nature in the form of chlorophyll which has a core ligand called chlorin, and heme with a core ligand called porphyrin. They add much of the colour seen in plants and humans. Phthalocyanine is an artificial macrocyclic tetradentate ligand that is used to make blue and green pigments.
In homogeneous catalysis, a C2-symmetric ligands usually describes bidentate ligands that are dissymmetric but not asymmetric by virtue of their C2-symmetry. Such ligands have proven valuable in catalysis. With C2 symmetry, C2-symmetric ligands limit the number of possible reaction pathways and thereby increase enantioselectivity, at least relative to asymmetrical analogues. Chiral ligands combine with metals to form chiral catalyst, which engages in a chemical reaction in which chirality is transfer to the reaction product. C2 symmetric ligands are a subset of chiral ligands.
