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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.
The term is mainly used in coordination chemistry. The template effects emphasizes the pre-organization provided by the coordination sphere, although the coordination modifies the electronic properties (acidity, electrophilicity, etc.) of ligands. [1] An early example is the dialkylation of a nickel dithiolate: [2]
The nucleophilicity of hydroxo ligands is relevant to the role of some M-OH centers in enzymology. For example, in carbonic anhydrase, a zinc hydroxide binds carbon dioxide: [7] L n M−OH + CO 2 ⇌ L n MO−O−CO 2 H. The oxygen evolving complex (OEC) consists of a Mn-Ca-O-OH cluster that is responsible for the biosynthesis of O 2. It is ...
Cisplatin, PtCl 2 (NH 3) 2, is a coordination complex of platinum(II) with two chloride and two ammonia ligands.It is one of the most successful anticancer drugs. 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 ...
In coordination chemistry, a macrocyclic ligand is a macrocyclic ring having at least nine atoms (including all hetero atoms) and three or more donor sites that serve as ligands. [1] Crown ethers and porphyrins are prominent examples. Macrocyclic ligands often exhibit high affinity for metal ions, the macrocyclic effect.
In coordination chemistry, the ligand cone angle (θ) is a measure of the steric bulk of a ligand in a transition metal coordination complex. It is defined as the solid angle formed with the metal at the vertex of a cone and the outermost edge of the van der Waals spheres of the ligand atoms at the perimeter of the base of the cone.
In coordination chemistry and crystallography, the geometry index or structural parameter (τ) is a number ranging from 0 to 1 that indicates what the geometry of the coordination center is. The first such parameter for 5-coordinate compounds was developed in 1984. [ 1 ]
Shilov cycle The overall charge is omitted from the complexes since the exact coordination sphere of the active species is unknown.. The Shilov system is a classic example of catalytic C-H bond activation and oxidation which preferentially activates stronger C-H bonds over weaker C-H bonds for an overall partial oxidation.