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cis-[CoCl2(NH3)4]
The
NH3 and Cl groups form a coordination sphere around the central cobalt ion. Cis-dichlorotetraamminecobalt(III).png](http://upload.wikimedia.org/wikipedia/commons/thumb/b/be/Cis-dichlorotetraamminecobalt%28III%29.png/220px-Cis-dichlorotetraamminecobalt%28III%29.png)
In coordination chemistry, the first coordination sphere refers to the array of molecules and ions (the ligands) directly attached to the central metal atom. The second coordination sphere consists of molecules and ions that attached in various ways to the first coordination sphere.
The first coordination sphere refers to the molecules that are attached directly to the metal. The interactions between the first and second coordination spheres usually involve hydrogen-bonding. For charged complexes, ion pairing is important.
In hexamminecobalt(III) chloride ([Co(NH3)6]Cl3), the cobalt cation plus the 6 ammonia ligands comprise the first coordination sphere. The coordination sphere of this ion thus consists of a central MN6 core "decorated" by 18 N−H bonds that radiate outwards.
![In crystalline FeSO4 7H2O, the first coordination sphere of Fe consists of six water ligands. The second coordination sphere consists of a water of crystallization and sulfate, which interact with the [Fe(H2O)6] centers. H-bondingFeSO47aq.tif](http://upload.wikimedia.org/wikipedia/commons/thumb/4/44/H-bondingFeSO47aq.tif/lossless-page1-342px-H-bondingFeSO47aq.tif.png)
Metal ions can be described as consisting of series of two concentric coordination spheres, the first and second. More distant from the second coordination sphere, the solvent molecules behave more like "bulk solvent." Simulation of the second coordination sphere is of interest in computational chemistry. The second coordination sphere can consist of ions (especially in charged complexes), molecules (especially those that hydrogen bond to ligands in the first coordination sphere) and portions of a ligand backbone. Compared to the first coordination sphere, the second coordination sphere has a less direct influence on the reactivity and chemical properties of the metal complex. Nonetheless the second coordination sphere is relevant to understanding reactions of the metal complex, including the mechanisms of ligand exchange and catalysis.
Mechanisms of metalloproteins often invoke modulation of the second coordination sphere by the protein. [1]
The rates at which ligands exchange between the first and the second coordination sphere is the first step in ligand substitution reactions. In associative ligand substitution, the entering nucleophile resides in the second coordination sphere. These effects are relevant to practical applications such as contrast agents used in MRI. [4]
The energetics of inner sphere electron transfer reactions are discussed in terms of second coordination sphere. Some proton coupled electron transfer reactions involve atom transfer between the second coordination spheres of the reactants:
Solvent effects on colors and stability are often attributable to changes in the second coordination sphere. Such effects can be pronounced in complexes where the ligands in the first coordination sphere are strong hydrogen-bond donors and acceptors, e.g. respectively [Co(NH3)6]3+ and [Fe(CN)6]3−. Crown-ethers bind to polyamine complexes through their second coordination sphere. Polyammonium cations bind to the nitrogen centres of cyanometallates. [5]
Macrocyclic molecules such as cyclodextrins act often as the second coordination sphere for metal complexes. [6] [7]
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.
Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO• is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.
Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.
In chemistry, an acid dissociation constant is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any species that has a filled orbital containing an electron pair which is not involved in bonding but may form a dative bond with a Lewis acid to form a Lewis adduct. For example, NH3 is a Lewis base, because it can donate its lone pair of electrons. Trimethylborane () is a Lewis acid as it is capable of accepting a lone pair. In a Lewis adduct, the Lewis acid and base share an electron pair furnished by the Lewis base, forming a dative bond. In the context of a specific chemical reaction between NH3 and Me3B, a lone pair from NH3 will form a dative bond with the empty orbital of Me3B to form an adduct NH3•BMe3. The terminology refers to the contributions of Gilbert N. Lewis.
In chemistry, a supramolecular assembly is a complex of molecules held together by noncovalent bonds. While a supramolecular assembly can be simply composed of two molecules, or a defined number of stoichiometrically interacting molecules within a quaternary complex, it is more often used to denote larger complexes composed of indefinite numbers of molecules that form sphere-, rod-, or sheet-like species. Colloids, liquid crystals, biomolecular condensates, micelles, liposomes and biological membranes are examples of supramolecular assemblies, and their realm of study is known as supramolecular chemistry. The dimensions of supramolecular assemblies can range from nanometers to micrometers. Thus they allow access to nanoscale objects using a bottom-up approach in far fewer steps than a single molecule of similar dimensions.
In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral.
In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia ligand. "Ammine" is spelled this way for historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.
Macrocycles are often described as molecules and ions containing a ring of twelve or more atoms. Classical examples include the crown ethers, calixarenes, porphyrins, and cyclodextrins. Macrocycles describe a large, mature area of chemistry.
Metal–organic frameworks (MOFs) are a class of porous polymers consisting of metal clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures. The organic ligands included are sometimes referred to as "struts" or "linkers", one example being 1,4-benzenedicarboxylic acid (BDC).
Transition metal dinitrogen complexes are coordination compounds that contain transition metals as ion centers the dinitrogen molecules (N2) as ligands.
In coordination chemistry, clathrochelates are ligands that encapsulate metal ions. Chelating ligands bind to metals more strongly than related monodentate ligands, and macrocyclic ligands bind more strongly than typical chelating ligands. It follows that bi- or polymacrocyclic ligands would bind to metals particularly strongly. Clathrochelates are usually derived from bimacrocyclic ligands.
In coordination chemistry, a stability constant is an equilibrium constant for the formation of a complex in solution. It is a measure of the strength of the interaction between the reagents that come together to form the complex. There are two main kinds of complex: compounds formed by the interaction of a metal ion with a ligand and supramolecular complexes, such as host–guest complexes and complexes of anions. The stability constant(s) provide(s) the information required to calculate the concentration(s) of the complex(es) in solution. There are many areas of application in chemistry, biology and medicine.
Associative substitution describes a pathway by which compounds interchange ligands. The terminology is typically applied to organometallic and coordination complexes, but resembles the Sn2 mechanism in organic chemistry. The opposite pathway is dissociative substitution, being analogous to the Sn1 pathway. Intermediate pathways exist between the pure associative and pure dissociative pathways, these are called interchange mechanisms.
Equilibrium chemistry is concerned with systems in chemical equilibrium. The unifying principle is that the free energy of a system at equilibrium is the minimum possible, so that the slope of the free energy with respect to the reaction coordinate is zero. This principle, applied to mixtures at equilibrium provides a definition of an equilibrium constant. Applications include acid–base, host–guest, metal–complex, solubility, partition, chromatography and redox equilibria.
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.
A metal ion in aqueous solution or aqua ion is a cation, dissolved in water, of chemical formula [M(H2O)n]z+. The solvation number, n, determined by a variety of experimental methods is 4 for Li+ and Be2+ and 6 for most elements in periods 3 and 4 of the periodic table. Lanthanide and actinide aqua ions have higher solvation numbers (often 8 to 9), with the highest known being 11 for Ac3+. The strength of the bonds between the metal ion and water molecules in the primary solvation shell increases with the electrical charge, z, on the metal ion and decreases as its ionic radius, r, increases. Aqua ions are subject to hydrolysis. The logarithm of the first hydrolysis constant is proportional to z2/r for most aqua ions.
Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.
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.
1,5-Diaza-3,7-diphosphacyclooctanes are organophosphorus compounds with the formula [R'NCH2P(R)CH2]2, often abbreviated PR2NR'2. They are air-sensitive white solids that are soluble in organic solvents. The ligands exist as meso and d,l-diastereomers, but only the meso forms function as bidentate ligands.