Transition metal sulfate complexes or sulfato complexes are coordination complexes with one or more sulfate ligands. Being the conjugate base of a strong acid (sulfuric acid), sulfate is not basic. It is more commonly a counterion in coordination chemistry, not a ligand.
Sulfate binds to metals through one, two, three, or all four oxygen atoms. [1]
Among the handful of complexes containing sulfate (or sulfato) ligands, most examples feature unidentate or chelating bidentate sulfate. Well characterized xamples are found with cobalt(III) ammines since these complexes are exchange inert. Monodentate sulfate is found in [Co(tren)(NH3)(SO4)]+ (tren = tris(2-aminoethyl)amine) [2] Although [Co(en)2O2SO2]+ is unknown, [(en)2Co(OS(O)2O)2Co(en)2]2+ forms instead (en = ethylenediamine). Bidentate sulfate is observed crystallographically in [Co(tetraamine)O2SO2]+. [3]
Sulfate function as a tridentate bridging ligand [Re3Cl9(SO4)]2−. [4]
All four oxygen atoms of sulfate bond to metals in some Dawson-type polyoxometalates, e.g. [S2Mo18O62]4-. [5]
Tutton's salts, with the formula M'2M(SO4)2(H2O)6 (M' = K+, etc.; M = Fe2+, etc.), illustrate the ability of water to outcompete sulfate as a ligand for M2+. Similarly alums, such as chrome alum ([K(H2O)6][Cr(H2O)6][SO4]2), features [Cr(H2O)6]3+ with noncoordinated sulfate. In a related vein, some sulfato complexes confirmed by X-ray crystallography, convert to simple aquo complexes when dissolved in water. Copper(II) sulfate examplifies this behavior, sulfate is bonded to copper in the crystal but dissociates upon dissolution.
![Structure of [Pt(NH3)4(NO)(SO4)] . Selected bond distances: Pt-O, 2.284; S-O range from 1.496 to 1.462 A. Color code: blue = N, red = O, dark blue = Pt. CSD CIF HUXMIX.png](http://upload.wikimedia.org/wikipedia/commons/thumb/7/78/CSD_CIF_HUXMIX.png/220px-CSD_CIF_HUXMIX.png)
Sulfato complexes are commonly produced by reaction of metal sulfates with other ligands.
In some cases, sulfato complexes are produced from sulfur dioxide: [7]
Sulfato complexes also arise by air-oxidation of metal sulfides. [8]
A dominant reaction of sulfato complexes is solvolysis, i.e. displacement of sulfate from the first coordination sphere by polar solvents such as water.
Sulfato complexes are susceptible to protonation of uncoordinated oxygen atoms. [9]
A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.
Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic red-brown solids. The soluble trihydrated (n = 3) salt is the usual compound of commerce. It is widely used to prepare compounds used in homogeneous catalysis.
In chemistry, hexol is a cation with formula {[Co(NH3)4(OH)2]3Co}6+ — a coordination complex consisting of four cobalt cations in oxidation state +3, twelve ammonia molecules NH
3, and six hydroxy anions HO−
, with a net charge of +6. The hydroxy groups act as bridges between the central cobalt atom and the other three, which carry the ammonia ligands.
Uranyl sulfate describes a family of inorganic compounds with the formula UO2SO4(H2O)n. These salts consist of sulfate, the uranyl ion, and water. They are lemon-yellow solids. Uranyl sulfates are intermediates in some extraction methods used for uranium ores. These compounds can also take the form of an anhydrous salt.
In coordination chemistry, hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated. In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity, and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands.
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.
Cobalt(II) sulfate is any of the inorganic compounds with the formula CoSO4(H2O)x. Usually cobalt sulfate refers to the hexa- or heptahydrates CoSO4.6H2O or CoSO4.7H2O, respectively. The heptahydrate is a red solid that is soluble in water and methanol. Since cobalt(II) has an odd number of electrons, its salts are paramagnetic.
In chemistry, metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlorates. They have the general stoichiometry [M(H2O)n]z+. Their behavior underpins many aspects of environmental, biological, and industrial chemistry. This article focuses on complexes where water is the only ligand, but of course many complexes are known to consist of a mix of aquo and other ligands.
Chromium(II) sulfate is an inorganic compound with the chemical formula CrSO4. It often comes as hydrates CrSO4·nH2O. Several hydrated salts are known. The pentahydrate CrSO4·5H2O is a blue solid that dissolves readily in water. Solutions of chromium(II) are easily oxidized by air to Cr(III) species. Solutions of Cr(II) are used as specialized reducing agents of value in organic synthesis.
The organic compound 3-pyridylnicotinamide (3-pna), also known as N-(pyridin-3-yl)nicotinamide, is a kinked dipodal dipyridine that is synthesized through the reaction of nicotinoyl chloride and 3-aminopyridine. The nitrogen atoms on its pyridine rings, like those of its isomer 4-pyridylnicotinamide, can donate their electron lone pairs to metal cations, allowing it to bridge metal centers and act as a bidentate ligand in coordination polymers. It can be used to synthesize polymers that have potentially useful gas adsorption properties.
Chloropentamminecobalt chloride is the dichloride salt of the coordination complex [Co(NH3)5Cl]2+. It is a red-violet, diamagnetic, water-soluble salt. The compound has been of academic and historical interest.
Transition metal amino acid complexes are a large family of coordination complexes containing the conjugate bases of the amino acids, the 2-aminocarboxylates. Amino acids are prevalent in nature, and all of them function as ligands toward the transition metals. Not included in this article are complexes of the amides and ester derivatives of amino acids. Also excluded are the polyamino acids including the chelating agents EDTA and NTA.
Transition metal carboxylate complexes are coordination complexes with carboxylate (RCO2−) ligands. Reflecting the diversity of carboxylic acids, the inventory of metal carboxylates is large. Many are useful commercially, and many have attracted intense scholarly scrutiny. Carboxylates exhibit a variety of coordination modes, most common are κ1- (O-monodentate), κ2 (O,O-bidentate), and bridging.
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.
Transition metal oxalate complexes are coordination complexes with oxalate (C2O42−) ligands. Some are useful commercially, but the topic has attracted regular scholarly scrutiny. Oxalate (C2O42-) is a kind of dicarboxylate ligand. As a small, symmetrical dinegative ion, oxalate commonly forms five-membered MO2C2 chelate rings. Mixed ligand complexes are known, e.g., [Co(C2O4)(NH3)4]κ+.
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.
Sodium tris(carbonato)cobalt(III) is the inorganic compound with the formula Na3Co(CO3)3•3H2O. The salt contains an olive-green metastable cobalt(III) coordination complex. The salt, a homoleptic metal carbonato complex, is sometimes referred to as the “Field-Durrant precursor” and is prepared by the “Field-Durrant synthesis”. It is used in the synthesis of other cobalt(III) complexes. Otherwise cobalt(III) complexes are generated from cobalt(II) precursors, a process that requires an oxidant.
Transition metal carbonate and bicarbonate complexes are coordination compounds containing carbonate (CO32-) and bicarbonate (HCO3-) as ligands. The inventory of complexes is large, enhanced by the fact that the carbonate ligand can bind metal ions in a variety of bonding modes. They illustrate the fate of low valent complexes when exposed to air.
Transition metal phosphate complexes are coordination complexes with one or more phosphate ligands. Phosphate binds to metals through one, two, three, or all four oxygen atoms. The bidentate coordination mode is common. The second and third pKa's of phosphoric acid, pKa2 and pKa3, are 7.2 and 12.37, respectively. It follows that HPO2−4 and PO3−4 are sufficiently basic to serve as ligands. The examples below confirm this expectation. Molecular metal phosphate complexes have no or few applications.
Hafnium(IV) sulfate is describes the inorganic chemical compounds with the formula Hf(SO4)2·nH2O, where n can range from 0 to 7. It commonly forms the anhydrous and tetrahydrate forms, which are both white solids.