![Structure of the metal nitrate complex [Rh(NO3)5] . Rh(NO3)52-.svg](http://upload.wikimedia.org/wikipedia/commons/thumb/c/ca/Rh%28NO3%2952-.svg/220px-Rh%28NO3%2952-.svg.png)
A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds. [2]
A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds. [2]
Being the conjugate base of a strong acid (nitric acid, pKa = -1.4), nitrate has modest Lewis basicity. Two coordination modes are common: unidentate and bidentate. Often, bidentate nitrate, denoted κ2-NO3, is bound unsymmetrically in the sense that one M-O distance is clearly bonding and the other is more weakly interacting. [2] The MO-N distances for the coordinated oxygen are longer by about 10 picometers longer than the N-Oterminal bonds. This observation suggests that the terminal N-O bonds have double bond character. Nitrate is isostructural with but less basic than carbonate. Both exhibit comparable coordination geometries. The nitrogen center of nitrate does not form bonds to metals.
With three terminal oxide groups, nitrate can in principle bind metals through many geometries. Even though the ligand is written as MNO3, the oxygen atoms are invariably coordinated. Thus, monodentate nitrate is illustrated by [Co(NH3)5NO3]2+, which could also be written as [Co(NH3)5ONO2]2+. Homoleptic metal nitrate complexes generally have O,O'-bidentate nitrate ligands.
| Formula | name | comment |
|---|---|---|
| Ti(NO3)4 | titanium(IV) nitrate | eight-coordinate, volatile |
| Co(NO3)3 | cobalt(III) nitrate | octahedral volatile |
| Cu(NO3)2 | copper(II) nitrate | planar, volatile |
| AgNO3 | silver nitrate | coordination polymer |
Typical metal nitrates are hydrated. Some of these salts crystallize with one or more nitrate ligands, but most are assumed to dissolve in water to give aquo complexes, often of the stoichiometry [M(H2O)6]n+.
Metal nitrate complexes are often prepared by treating metal oxides or metal carbonates with nitric acid. The main complication with dissolving metals in nitric acid arises from redox reactions, which can afford either nitric oxide or nitrogen dioxide.
Anhydrous nitrates can be prepared by the oxidation of metals with dinitrogen tetroxide (often as a mixture with nitrogen dioxide, with which it interconverts). N2O4 undergoes molecular autoionization to give [NO+] [NO3−], with the former nitrosonium ion being a strong oxidant. The method is illustrated by the route to β-Cu(NO3)2:
Many metals, metal halides, and metal carbonyls undergo similar reactions, but the product formulas can be deceptive. For example from chromium one obtains Cr(NO3)3(N2O4)2, which was shown to be the salt (NO+)2[Cr(NO3)5]2-. [15] Nitrogen oxides readily interconvert between various forms, some of which may act as completing ligands. The redox reaction of nitrosonium and the metal can give rise to nitrogen oxide which forms strong metal nitrosyl complexes; nitronium ions (NO2+) are similarly observed. [16]
In some cases, nitrate complexes are produced from the reaction of nitrogen dioxide with a metal dioxygen complex: [17]
Given nitrate's low basicity, the tendency of metal nitrate complexes toward hydrolysis is expected. Thus copper(II) nitrate readily dissociates in aqueous solution to give the aqua complex:
Pyrolysis of metal nitrates yields oxides. [18]
This reaction is used to impregnate oxide supports with nickel oxides.
Nitrate reductase enzymes convert nitrate to nitrite. The mechanism involves the intermediacy of Mo-ONO2 complexes. [19]
Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.
Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russian rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.
Lead(II) nitrate is an inorganic compound with the chemical formula Pb(NO3)2. It commonly occurs as a colourless crystal or white powder and, unlike most other lead(II) salts, is soluble in water.
Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.
Copper(II) nitrate describes any member of the family of inorganic compounds with the formula Cu(NO3)2(H2O)x. The hydrates are blue solids. Anhydrous copper nitrate forms blue-green crystals and sublimes in a vacuum at 150-200 °C. Common hydrates are the hemipentahydrate and trihydrate.
In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.
Zinc nitrate is an inorganic chemical compound with the formula Zn(NO3)2. This colorless, crystalline salt is highly deliquescent. It is typically encountered as a hexahydrate Zn(NO3)2·6H2O. It is soluble in both water and alcohol.
Cadmium nitrate describes any of the related members of a family of inorganic compounds with the general formula Cd(NO3)2·xH2O. The most commonly encountered form being the tetrahydrate.The anhydrous form is volatile, but the others are colourless crystalline solids that are deliquescent, tending to absorb enough moisture from the air to form an aqueous solution. Like other cadmium compounds, cadmium nitrate is known to be carcinogenic. According to X-ray crystallography, the tetrahydrate features octahedral Cd2+ centers bound to six oxygen ligands.
Iron(III) nitrate, or ferric nitrate, is the name used for a series of inorganic compounds with the formula Fe(NO3)3.(H2O)n. Most common is the nonahydrate Fe(NO3)3.(H2O)9. The hydrates are all pale colored, water-soluble paramagnetic salts.
The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.
Nickel nitrate is the inorganic compound Ni(NO3)2 or any hydrate thereof. In the hexahydrate, the nitrate anions are not bonded to nickel. Other hydrates have also been reported: Ni(NO3)2.9H2O, Ni(NO3)2.4H2O, and Ni(NO3)2.2H2O.
Chromium(III) nitrate describes several inorganic compounds consisting of chromium, nitrate and varying amounts of water. Most common is the dark violet hygroscopic solid. An anhydrous green form is also known. Chromium(III) nitrate compounds are of a limited commercial importance, finding some applications in the dyeing industry. It is common in academic laboratories for the synthesis of chromium coordination complexes.
Manganese(II) nitrate refers to the inorganic compounds with formula Mn(NO3)2·(H2O)n. These compounds are nitrate salts containing varying amounts of water. A common derivative is the tetrahydrate, Mn(NO3)2·4H2O, but mono- and hexahydrates are also known as well as the anhydrous compound. Some of these compounds are useful precursors to the oxides of manganese. Typical of a manganese(II) compound, it is a paramagnetic pale pink solid.
Bismuth(III) nitrate is a salt composed of bismuth in its cationic +3 oxidation state and nitrate anions. The most common solid form is the pentahydrate. It is used in the synthesis of other bismuth compounds. It is available commercially. It is the only nitrate salt formed by a group 15 element, indicative of bismuth's metallic nature.
Cerium nitrate refers to a family of nitrates of cerium in the +3 or +4 oxidation state. Often these compounds contain water, hydroxide, or hydronium ions in addition to cerium and nitrate. Double nitrates of cerium also exist.
Titanium nitrate is the inorganic compound with formula Ti(NO3)4. It is a colorless, diamagnetic solid that sublimes readily. It is an unusual example of a volatile binary transition metal nitrate. Ill defined species called titanium nitrate are produced upon dissolution of titanium or its oxides in nitric acid.
Thorium(IV) nitrate is a chemical compound, a salt of thorium and nitric acid with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a salt of thorium it is weakly radioactive.
Nitrate chlorides are mixed anion compounds that contain both nitrate (NO3−) and chloride (Cl−) ions. Various compounds are known, including amino acid salts, and also complexes from iron group, rare-earth, and actinide metals. Complexes are not usually identified as nitrate chlorides, and would be termed chlorido nitrato complexes.
Nitratoauric acid, hydrogen tetranitratoaurate, or simply called gold(III) nitrate is a crystalline gold compound that forms the trihydrate, HAu(NO3)4·3H2O or more correctly H5O2Au(NO3)4·H2O. This compound is an intermediate in the process of extracting gold. In older literature it is also known as aurinitric acid.
In organometallic chemistry, transition metal complexes of nitrite describes families of coordination complexes containing one or more nitrite ligands. Although the synthetic derivatives are only of scholarly interest, metal-nitrite complexes occur in several enzymes that participate in the nitrogen cycle.