Name: coordination complexes and chelation
Uploaded: 2020-09-24T15:06:53.000Z
Duration: 2 min 51 s
Channel: JoVE

K12 Standards

new-york-state-science-learning-standards

New York State Science Learning Standards

High School

Physical Science

HS. Structure and Properties of Matter

HS-PS2-6.

Metal-Ligand Bonds

錯体イオンでは、金属イオンは配位子として知られるアニオン性または中性分子に結合しています。配位子は、1つ以上の孤立電子対の電子を持ち、電子対ドナーまたはルイス塩基として機能します。彼らは電子対を金属イオンに供与し、金属イオンは電子対受容体またはルイス酸として機能します。したがって、金属イオンと配位子との間の配位共有結合は、ルイス酸-塩基付加体を形成します。
電子対を供与する配位子原子は、ドナー原子として知られています。金属イオンを取り巻くドナー原子の数は、金属イオンの配位数と相関しています。
存在するドナー原子の数に応じて、リガンドはさらに単座、二座、または多座リガンドに分類され、荷電または中性にすることができます。
単座リガンドは、ドナー原子を1つだけ持っています。酸素は、中性の水分子のドナー原子です。窒素は、荷電したシアン化物イオンのドナー原子です。
二座配位子は、金属イオンに同時に結合するのに十分な距離にある2つのドナー原子を持っています。3つのビピリジン分子の窒素原子は、配位番号6のルテニウムイオンに結合します。
多座配位子は、その構造に2つ以上のドナー原子が存在します。ここでは、2分子のジエチレントリアミンから6つの窒素がコバルトイオンに結合します。
複数のドナー原子が中心の金属イオンを爪のように保持しているように見えるため、二座配位子と多座配位子はキレート剤とも呼ばれます。
キレート剤は、単座配位子よりも中心金属イオンに対する親和性が高く、より安定した配位錯体を形成します。これはキレート効果として知られています。
キレート剤は汎用性があります。これらは、反応中の干渉金属イオンを錯体化するために使用され、分解反応の触媒に関与する微量金属イオンを錯体化したり、エチレンジアミン四酢酸またはEDTAを使用して鉛中毒を治療したりすることで、食品の貯蔵寿命を延ばします。
錯体イオンの形成は、酸化電位や還元電位、色の変化など、金属イオンと配位子の物理化学的特性に影響を与えます。さらに、配位子は、水和金属イオンの脱プロトン化や、強く引き付けられた別の配位子による置換などの反応を起こすことがあります。ここでは、水分子がアンモニアに置き換えられ、アンモニアが金属イオンに強く結合します。

金属配位結合

血液中のヘモグロビン、葉緑素中のクロロフィル、ビタミンB-12、ポリエチレンなどの製造に使われる触媒には、すべて配位化合物が含まれています。金属、特に遷移金属のイオンは、錯体を形成しやすいです。
 これらの錯体では、遷移金属が配位共有結合を形成しています。これは、結合中の電子の両方がドナー（ルイス塩基）から電子アクセプター（ルイス酸）へと供与されているルイス酸-塩基相互作用の一種です。配位錯体におけるルイス酸は、中心金属イオン（または中心原子）であり、遷移金属または内側遷移金属からなります。ルイス塩基の電子供与体は配位子と呼ばれ、原子、分子、イオンなど様々な化学種からなります。唯一の条件は、中心金属に供与できる1つ以上の電子対を持っていることです。多くの場合、孤立電子対を持つドナー原子が、金属と配位結合を形成します。配位圏は、中心となる金属イオンまたは原子と、それに付随する配位子から構成されます。式中の括弧は配位圏を囲んでおり、括弧の外側の化学種は配位圏に含まれません。
 配位子が中心の金属と1つの原子だけで結合している場合を単座といい、これはギリシャ語の “one-toothed (1つの歯)”という語句に由来します。この場合、配位子の数と配位数は同じです。NH3、Cl−、H2Oのようにドナー原子が1つの配位子は単座配位子です。他の多くの配位子は、より複雑な形で金属に配位します。
 二座配位子とは、金属中心に2つの原子が配位するものです。例えば、エチレンジアミン（en, H2NCH2CH2NH2）は、2つの窒素原子を含んでおり、それぞれが孤立電子対を持ったルイス塩基として機能する（Figure 1a）。この2つの窒素原子はいずれも単独の金属中心に配位することができます。錯体[Co(en)3]3+では、2座のen配位子が3つあり、コバルト(III)イオンの配位数は6である（Figure 1b）。最も一般的な配位数は2、4、6ですが、1から15までのあらゆる配位数の例が知られています。
 <img alt="Image1" src="/files/ftp_upload/11456/11456_Image_1.svg" style="text-align: center; height: 200px;" />
 Figure 1. (a) エチレンジアミン (en) は、金属イオンと配位可能な2つの窒素原子（それぞれ1つの孤立電子対を持つ）を含む。 (b) 3つの二座en配位子が1つのコバルトイオンに配位しています。
 中心の金属イオンに2つ以上のドナー原子で結合する配位子は、2つ以上の結合で金属に配座するため、多座配位子（または “many teeth”）と呼ばれます。ギリシャ語の「爪」を意味するキレートという言葉も、この種の配位相互作用を表すのに用いられます。多くの多座配位子はキレート配位子であり、これらの配位子の1つまたは複数と中心金属からなる錯体をキレート錯体と呼びます。キレート配位子はキレート剤ともいいます。キレート配位子は、カニの爪がビー玉を押さえるように金属イオンを保持します。多座配位子には、ドナー原子の数を示す接頭辞が付くことがあります。ヘモグロビンのヘム複合体もその一つです（Figure 2）。ヘム複合体には、鉄と結合する4つのドナー原子を持つ多座配位子が含まれています。
 <img alt="Image2" src="/files/ftp_upload/11456/11456_Image2.svg" style="text-align: center; height: 200px;" />
 Figure 2:  単一の配位子であるヘムには4つの窒素原子が含まれており、ヘモグロビンの鉄に配位してキレート錯体を形成します。
 上記の文章は以下から引用しました。 <a href="https://openstax.org/books/chemistry-2e/pages/19-2-coordination-chemistry-of-transition-metals">Openstax, Chemistry 2e, Chapter 19.2 Coordination Chemistry of Transition Metals</a>.

血液中のヘモグロビン、緑の植物のクロロフィル、ビタミンB-12、およびポリエチレンの製造に使用される触媒はすべて含まれています...

Education

JoVE Core

Chemistry

化学

Transition Metals and Coordination Complexes

遷移金属と配位錯体

transition-metals-and-coordination-complexes

KEY TERMS AND CONCEPTS

主要用語と概念

coordination complexes and chelation

Coordination complexes form when a metal ion bonds to ligands. These compounds appear in familiar examples such as hemoglobin in blood, chlorophyll in green plants, vitamin B-12, and the catalyst used to make polyethylene. Transition metal ions are especially likely to form these complexes.

In a coordination complex, the metal acts as a Lewis acid. The ligand acts as a Lewis base and donates both electrons in the coordinate covalent bond. A ligand can be an atom, molecule, or ion, as long as it has one or more electron pairs to share with the metal. The central metal ion or atom, along with its attached ligands, makes up the coordination sphere. Brackets in a formula show the coordination sphere, and anything outside the brackets is not part of it.

Ligands can bind in different ways. Monodentate ligands connect through only one atom, so the number of ligands equals the coordination number. Common examples are NH3, Cl−, and H2O. Bidentate ligands bind through two atoms. Ethylenediamine, or en, has two nitrogen atoms with lone pairs that can both bond to one metal center. In the complex [Co(en)3]3+, three bidentate ligands give cobalt(III) a coordination number of six.

Ligands that attach through more than one donor atom are called polydentate ligands. The word chelate comes from a Greek word meaning “claw,” and it describes how these ligands hold a metal ion. A complex with one or more chelating ligands is called a chelate, and a chelating ligand is also called a chelating agent. These ligands can be identified with prefixes that show the number of donor atoms they use.

The heme complex in hemoglobin is another key example. Heme is a single polydentate ligand with four donor atoms, and all four coordinate to iron. Coordination numbers in complexes are often 2, 4, or 6, but examples from 1 to 15 are known. These bonding patterns help explain the structure of many important metal-containing compounds.

Coordination Complexes and Chelation

properties of transition metals

Transition Metals in the Periodic Table

Transition metals are the d-block elements and the inner transition metals in the f-block. They are defined by partially filled d orbitals. In the periodic table, the transition elements are in groups 3 through 11, and the inner transition metals appear in the two rows below the main body of the table. The d-block is often grouped into transition series. The first transition series runs from Sc through Cu. The second series runs from Y through Ag. The third series includes La and Hf through...

coordination compounds and nomenclature

How Transition Metal Complexes Are Named

Transition metal complexes are named by following rules for ligands, metal ions, and oxidation state. These compounds form when a central metal ion or atom, often a transition metal or inner transition metal, accepts electron pairs from ligands. A ligand is a Lewis base that can be an atom, molecule, or ion with one or more lone pairs to donate. In these complexes, the bond is a coordinate covalent bond. That means both electrons in the bond come from the donor, such as ammonia, and are...

metal-ligand bonds

Coordination complexes form when a metal ion bonds to ligands. These compounds appear in familiar examples such as hemoglobin in blood, chlorophyll in green plants, vitamin B-12, and the catalyst used to make polyethylene. Transition metal ions are especially likely to form these complexes. In a coordination complex, the metal acts as a Lewis acid. The ligand acts as a Lewis base and donates both electrons in the coordinate covalent bond. A ligand can be an atom, molecule, or ion, as long as...

coordination number and geometry

Transition Metal Shapes from Coordination Number

Transition metal complexes are often identified by their coordination number and the shape around the metal ion. The coordination number is the number of donor atoms bonded to the central metal. In many complexes, the most common shapes are octahedral, tetrahedral, and square planar. Coordination number and molecular geometry are linked in a clear pattern. A coordination number of 2 gives a linear shape, as in [Ag(NH3)2]+. A coordination number of 3 gives a trigonal planar shape, as in...

structural isomerism

Linkage and Ionization Isomers

Isomers are different chemical species that share the same chemical formula. In coordination compounds, structural isomerism includes linkage isomers and coordination-sphere isomers. These two forms show how the same atoms can be arranged in different ways around a metal center. Linkage isomers form when a ligand can attach to a transition metal through two different atoms. The cyanide ligand, CN−, can bind through carbon or nitrogen. The thiocyanate ligand, SCN−, can bind through sulfur or...

stereoisomerism

Isomer Shapes in Coordination Complexes

Isomer shapes in coordination complexes can change a compound’s properties even when the chemical formula stays the same. Isomers are different chemical species with the same formula. In transition metal complexes, the atoms stay connected through the same types of bonds, but their arrangement in space can differ. One common form is geometric isomerism. In these complexes, ligands (the ions or molecules attached to the metal) can sit in cis or trans positions. The octahedral [Co(NH3)4Cl2]+ ion...

valence bond theory

Metal Ligand Bonds in Coordination Complexes

Coordination complexes form metal-ligand bonds through valence bond theory. In this model, Linus Pauling explained bonding with hybridization and overlap of atomic orbitals. The central metal atom or ion acts as a Lewis acid. It uses empty orbitals of suitable energy to accept electron pairs from ligands, which act as Lewis bases. These coordinate covalent bonds help explain the color, geometry, and magnetic behavior seen in coordination compounds. The type of hybridization helps determine the...

crystal field theory - octahedral complexes

crystal-field-theory-octahedral-complexes

Octahedral d-Orbital Splitting in Crystal Fields

Crystal field theory explains how ligands affect the d orbitals in transition metal complexes. This electrostatic model helps predict the colors, magnetic behavior, and some structures of coordination compounds. It focuses on the nonbonding electrons on the central metal ion, not on the metal-ligand bonds. In crystal field theory, the metal ion and ligands are treated as very small point charges. Because electrons are negative, electrons donated by the ligands repel the electrons in the...

crystal field theory - tetrahedral and square planar complexes

crystal-field-theory-tetrahedral-and-square-planar-complexes

Crystal Field Splitting in Non-Octahedral Shapes

Crystal field theory also explains d orbital splitting in tetrahedral and square planar complexes. These shapes do not follow the same pattern as an octahedral complex, so the d orbitals respond to ligand placement in different ways. In tetrahedral complexes, the four ligands sit between the axes. None of the d orbitals points directly at the ligands, but the d x2−y2 and d z2 orbitals lie along the Cartesian axes and overlap less with the ligands than the d xy, d xz, and d yz orbitals. The d...

colors and magnetism

Color and Spin in Coordination Complexes

Color in coordination complexes comes from how metal electrons absorb light. When atoms or molecules absorb light at the right frequency, electrons move to higher-energy orbitals. For many main-group atoms and molecules, the absorbed light is ultraviolet and cannot be seen. In coordination compounds, the energy gap between d orbitals often matches visible light, so the compound can absorb and emit colors that the human eye detects. Small changes in orbital energy can cause large shifts in the...

key terms and concepts

Explore coordination complexes, ligand types, coordination numbers, and chelation using examples like hemoglobin, chlorophyll, and heme for high school chemistry.

Coordination Complexes and Chelation | JoVE K12

chemistry

JoVE Core 化学は、簡潔で理解しやすいアニメーションビデオレッスンを使用して、一般的な化学の概念を生き生きとしたものにします。さらに、活動する科学者のビデオでは、現在世界中の実験室で行われている古典的そして独創的な研究・実験をお見せします。

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Coordination Complexes and Chelation

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