配位圏

WordNet

a particular environment or walk of life; "his social sphere is limited"; "it was a closed area of employment"; "hes out of my orbit" (同)domain, area, orbit, field, arena
a solid figure bounded by a spherical surface (including the space it encloses)
a three-dimensional closed surface such that every point on the surface is equidistant from the center
any spherically shaped artifact
the geographical area in which one nation is very influential (同)sphere of influence
the grammatical relation of two constituents having the same grammatical form
the regulation of diverse elements into an integrated and harmonious operation
being of coordinate importance, rank, or degree
the skillful and effective interaction of movements

PrepTutorEJDIC

『球』,球体,球面 / (惑星・星などの)『天体』;天球;《詞》天,空 / (知識・活動・影響などの)『範囲』,領域《+『of』+『名』》 / (社会的)地位,階級
同等[にすること] / (筋肉運動の)整合,釣り合い

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2012/12/18 10:08:35」(JST)

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cis-[CoCl₂(NH₃)₄]⁺

The colored atoms form a coordination sphere around the ion of cobalt

In coordination chemistry, the coordination sphere refers to a central atom or ion and an array of molecules or anions, the ligands, around. ^[1] ^[2] Molecules that are attached noncovalently to the ligands are called the second coordination sphere.

First coordination sphere

The first coordination sphere refers to the molecules that are attached directly to the metal. These molecules are typically solvent. The interactions between the first and second coordination spheres usually involve hydrogen-bonding. For charged complexes, ion-pairing is important.

Hexamminecobalt(III) chloride

([Co(NH₃)₆]Cl₃)

In hexamminecobalt(III) chloride ([Co(NH₃)₆]Cl₃), the cobalt cation plus the six ammonia ligands comprise the first coordination sphere. The coordination sphere of this ion thus consists of a central MN₆ core "decorated" by 24 N-H bonds that radiate outwards.

Second coordination sphere

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 lessdirect 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.

Role in metalloenzymology

Mechanisms of metalloproteins often invoke modulation of the second coordination sphere by the protein. For example, an amine cofactor in the second coordination sphere of some hydrogenase enzymes assists in the activation of dihydrogen substrate.^[3]

Role in mechanistic inorganic chemistry

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:

[Fe*(H₂O)₆]²⁺ + [Fe(H₂O)₅(OH)]²⁺ → [Fe(H₂O)₆]³⁺ + [Fe*(H₂O)₅(OH)]²⁺

Role in spectroscopy

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]

References

^ chemistry-dictionary.com - Definition of coordination sphere
^ What Is A Coordination Compound?
^ J. C. Fontecilla-Camps, A. Volbeda, C. Cavazza, Y. Nicolet "Structure/Function Relationships of [NiFe]- and [FeFe]-Hydrogenases" Chem. Rev. 2007, 107, 4273-4303. doi:10.1021/cr050195z
^ R. M. Supkowski, W. DeW. Horrocks Jr. "On the determination of the number of water molecules, q, coordinated to europium(III) ions in solution from luminescence decay lifetimes" Inorganic Chimica Acta 2002, Volume 340, pp. 44–48. doi:10.1016/S0020-1693(02)01022-8
^ Lehn, J. M. Supramolecular Chemistry: Concepts and Perspectives; VCH: Weinhiem, 1995.

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English Journal

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Hoffmann KM, Samardzic D, Heever K, Rowlett RS.SourceDepartment of Chemistry, Colgate University, 13 Oak Drive, Hamilton, NY 13346, USA.
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Cobalt(II)-substituted Haemophilus influenzae β-carbonic anhydrase (HICA) has been produced by overexpression in minimal media supplemented with CoCl(2), enabling kinetic, structural, and spectroscopic characterization. Co(II)-substituted HICA (Co-HICA) has comparable catalytic activity to that of
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The electronic structures of the S(2) states of the oxygen-evolving complexes of photosystem II in plants and cyanobacteria in the presence and absence of methanol.

Su JH, Cox N, Ames W, Pantazis DA, Rapatskiy L, Lohmiller T, Kulik LV, Dorlet P, Rutherford AW, Neese F, Boussac A, Lubitz W, Messinger J.SourceMax-Planck-Institut fur Bioanorganische Chemie, Stiftstrasse 34-36, D-45470 Mulheim an der Ruhr, Germany.
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The electronic properties of the Mn(4)O(x)Ca cluster in the S(2) state of the oxygen-evolving complex (OEC) were studied using X- and Q-band EPR and Q-band (55)Mn-ENDOR using photosystem II preparations isolated from the thermophilic cyanobacterium T. elongatus and higher plants (spinach). The data
PMID 21406177

Japanese Journal

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山崎朗
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NAID 110007539081

Hydrolysis Constant and Coordination Geometry of Zirconium(IV)

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Journal of nuclear science and technology 45(8), 735-739, 2008-08-01
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NAID 10021367615