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

K12 Standards

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New York State Science Learning Standards

High School

Physical Science

HS. Structure and Properties of Matter

HS-PS2-6.

Metal-Ligand Bonds

In einem komplexen Ion ist das Metallion an anionische oder neutrale Moleküle, sogenannte Liganden, gebunden. Liganden haben ein oder mehrere einsame Elektronenpaare und fungieren als Elektronenpaardonatoren oder Lewis-Basen. Sie geben das Elektronenpaar an das Metallion ab, das als Elektronenpair-Akzeptor oder Lewis-Säure fungiert. So bildet eine kovalente Koordinatenbindung zwischen dem Metallion und dem Liganden ein Lewis-Säure-Base-Addukt.
Das Ligandenatom, das ein Elektronenpaar abgibt, wird als Donoratom bezeichnet. Die Anzahl der Donoratome, die das Metallion umgeben, korreliert mit der Koordinationszahl des Metallions.
Abhängig von der Anzahl der vorhandenen Donoratome werden Liganden weiter in einzähnige, zweizähnige oder mehrzähnige Liganden eingeteilt, die geladen oder neutral sein können.
Monodentate Liganden haben nur ein Donoratom. Sauerstoff ist ein Donoratom in einem neutralen Wassermolekül; Stickstoff ist ein Donoratom in einem geladenen Cyanid-Ion.
Zweizähnige Liganden haben zwei Donoratome, die weit genug voneinander entfernt sind, um gleichzeitig an ein Metallion zu binden. Die Stickstoffatome von drei Bipyridin-Molekülen binden an ein Ruthenium-Ion mit der Koordinationszahl sechs.
Ein polyzähnierter Ligand hat zwei oder mehr Donoratome, die in seiner Struktur vorhanden sind. Dabei binden sechs Stickstoffe aus zwei Molekülen Diethylentriamin an ein Kobalt-Ion.
Da mehrere Donoratome das zentrale Metallion wie eine Klaue zu halten scheinen, werden die zweizähnigen und mehrzähnigen Liganden auch als Chelatbildner bezeichnet.
Ein Chelatbildner hat eine höhere Affinität zum zentralen Metallion als ein einzähniger Ligand und bildet einen stabileren Koordinationskomplex. Dies ist als chelatbildender Effekt bekannt.
Chelatbildner sind vielseitig einsetzbar. Sie werden verwendet, um störende Metallionen in einer Reaktion zu komplexieren – um die Haltbarkeit von Lebensmitteln zu erhöhen, indem Spurenmetallionen, die an der Katalyse von Zersetzungsreaktionen beteiligt sind, komplexiert werden oder Bleivergiftungen mit Ethylendiamintetraacetat oder EDTA behandelt werden.
Die Bildung von Komplexionen beeinflusst die physikalisch-chemischen Eigenschaften der Metallionen und Liganden, wie z.B. die Änderung des Oxidations- und Reduktionspotentials oder der Farben. Darüber hinaus können Liganden Reaktionen wie die Deprotonierung hydratisierter Metallionen oder die Verdrängung durch einen anderen stark angezogenen Liganden durchlaufen. Hier wird das Wassermolekül durch Ammoniak ersetzt, das stärker an das Metallion bindet.

metall-ligand-bindungen

Das Hämoglobin im Blut, das Chlorophyll in grünen Pflanzen, Vitamin B-12 und der Katalysator, der bei der Herstellung von Polyethylen verwendet wird, enthalten allesamt Koordinationsverbindungen. Ionen der Metalle, insbesondere der Übergangsmetalle, neigen dazu, Komplexe zu bilden. In diesen Komplexen bilden Übergangsmetalle koordinative kovalente Bindungen, eine Art Lewis-Säure-Base-Wechselwirkung, bei der beide Elektronen in der Bindung von einem Donor (Lewis-Base) an einen Elektronenakzeptor (Lewis-Säure) abgegeben werden. Die Lewis-Säure in Koordinationskomplexen, oft als zentrales Metallion (oder Atom) bezeichnet, ist das Übergangsmetall oder innere Übergangsmetall. Die Lewis-Basen-Donoren, sogenannte Liganden, können eine Vielzahl von Chemikalien sein – Atome, Moleküle oder Ionen. Die einzige Voraussetzung ist, dass sie über ein oder mehrere Elektronenpaare verfügen, die an das Zentralmetall abgegeben werden können. Meistens handelt es sich dabei um ein Donoratom mit einem freien Elektronenpaar, das eine koordinative Bindung zum Metall eingehen kann. Die Koordinationssphäre besteht aus dem zentralen Metallion oder -atom und den daran gebundenen Liganden. Klammern in einer Formel schließen die Koordinationssphäre ein; Arten außerhalb der Klammern sind nicht Teil der Koordinationssphäre. Liganden sind monodentat (griechisch für „einzahnig“), wenn sie nur über ein Atom mit dem Zentralmetall verbunden sind. Dabei sind die Anzahl der Liganden und die Koordinationszahl gleich. Liganden mit einem Donoratom, wie NH3, Cl− und H2O, sind monodentat. Viele andere Liganden koordinieren auf komplexere Weise mit dem Metall. Zweizähnige Liganden sind solche, bei denen zwei Atome an das Metallzentrum koordinieren. Beispielsweise enthält Ethylendiamin (en, H2NCH2CH2NH2) zwei Stickstoffatome, von denen jedes ein freies Elektronenpaar aufweist und als Lewis-Base dienen kann (Figure 1a). Beide Atome können an ein einziges Metallzentrum koordinieren. Im Komplex [Co(en)3]3+ gibt es drei zweizähnige en-Liganden und die Koordinationszahl des Cobalt(III)-Ions beträgt sechs (Figure 1b). Die gebräuchlichsten Koordinationszahlen sind zwei, vier und sechs, es sind jedoch Beispiele für alle Koordinationszahlen von 1 bis 15 bekannt. <img alt="Image1" src="/files/ftp_upload/11456/11456_Image_1.svg" style="text-align: center; height: 200px;"> Figure 1. (a) Ethylendiamin (en) enthält zwei Stickstoffatome mit jeweils einem freien Elektronenpaar, die mit einem Metallion koordinieren können. (b) Drei zweizähnige Liganden koordinieren mit einem einzelnen Kobaltion. Jeder Ligand, der über mehr als ein Donoratom an ein zentrales Metallion bindet, ist ein mehrzähniger Ligand (oder „viele Zähne“), da er mit mehr als einer Bindung in das Metallzentrum eingreifen kann. Zur Beschreibung dieser Art der Interaktion wird auch der Begriff Chelat aus dem Griechischen für „Klaue“ verwendet. Viele mehrzähnige Liganden sind Chelatliganden, und ein Komplex, der aus einem oder mehreren dieser Liganden und einem Zentralmetall besteht, ist ein Chelat. Ein Chelatligand wird auch als Chelatbildner bezeichnet. Ein Chelatligand hält das Metallion so, wie eine Krabbenschere eine Murmel halten würde. Mehrzähnige Liganden werden manchmal mit Präfixen gekennzeichnet, die die Anzahl der Donoratome im Liganden angeben. Der Hämkomplex im Hämoglobin ist ein weiteres wichtiges Beispiel (Figure 2). Es enthält einen mehrzähnigen Liganden mit vier Donoratomen, die an Eisen koordinieren. <img alt="Image2" src="/files/ftp_upload/11456/11456_Image2.svg" style="text-align: center; height: 200px;"> Figure 2: Der einzelne Ligand Häm enthält vier Stickstoffatome, die sich an Eisen im Hämoglobin koordinieren und so ein Chelat bilden. Dieser Text wurde angepasst von <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>.

Metall-Ligand-Bindungen

Das Hämoglobin im Blut, das Chlorophyll in grünen Pflanzen, Vitamin B-12 und der Katalysator, der bei der Herstellung von Polyethylen verwendet wird, enthalten alle ...

Education

Lehre

JoVE Core

Chemistry

Chemie

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Transition Metals and Coordination Complexes

Übergangsmetalle und Koordinationskomplexe

transition-metals-and-coordination-complexes

KEY TERMS AND CONCEPTS

KERNBEGRIFFE UND KONZEPTE

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

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Coordination Complexes and Chelation

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