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

Num íon complexo, o íon metálico é ligado a moléculas aniónicas ou neutras, conhecidas como ligantes. Os ligantes têm um ou mais pares Solitários de elétrons e atuam como pares de elétrons doadores ou bases Lewis. Eles doam o par de elétrons ao íon metálico, que atua como um par de elétrons aceitante ou um ácido Lewis.Assim, uma ligação coordenada covalente entre o íon metálico e a ligante forma um aduto Lewis de base ácida. A doação ao átomo do ligante de um par de elétrons é conhecido como o átomo dador. O número de átomos dadores ao redor do íon metálico está correlacionado com o número de coordenação do íon metálico.Consoante o número de átomos dos dadores presentes, os ligantes são posteriormente classificados como monodentado, bidentado, ou polidentados, que podem ter carga ou serem neutros. Os ligantes monodentados têm apenas um átomo dador. O oxigénio é um átomo dador numa molécula de água neutra;o nitrogénio é um átomo dador num íon de cianeto carregado.Os ligantes bidentados têm dois átomos dadores que estão suficientes afastados para se ligarem simultaneamente a um íon metálico. Os átomos de azoto de três moléculas de bipiridina ligam-se a um íon de ruténio com o número de coordenação seis. Um ligante polidentado tem dois ou mais átomos dadores presente na sua estrutura.Aqui, seis nitrogênios a partir de duas moléculas de dietilenotriamina ligam-se a um íon de cobalto. À medida que aparecem múltiplos átomos dadores para segurar o íon metálico central como uma garra, os ligantes bidentados e polidentados são também chamados de agentes quelantes. Um agente quelante tem mais afinidade com o íon metálico central do que um ligante monodentado, um complexo de coordenação mais estável.Isto é conhecido como o efeito quelante. Os agentes quelantes são versáteis. Estão habituados a complexar íons metálicos interferentes numa reação para aumentar o prazo de validade dos produtos alimentares pelos íons metálicos vestigiais complexantes envolvidos nas reações de decomposições catalíticas ou tratamento de envenenamento por chumbo utilizando etilenodiaminotetracetato ou EDTA.A complexa formação iónica influencia as propriedades físico-químicas do íon metálico e ligantes, tais como a alteração na oxidação e os potenciais de redução ou cores. Além disso, os ligantes podem ser submetidos a reações como a deprotonação dos íons de metal hidratado ou deslocamento por outro ligante fortemente atraído. Aqui, a molécula da água é substituída por amoníaco, que se liga mais fortemente ao íon metálico.

ligações metal-ligando

A hemoglobina no sangue, a clorofila em plantas verdes, a vitamina B-12, e o catalisador utilizado na fabricação do polietileno contêm todos compostos de coordenação. Os iões dos metais, especialmente os metais de transição, são susceptíveis de formar complexos.
Nesses complexos, os metais de transição formam ligações covalentes coordenadas, uma espécie de interação ácido-base de Lewis na qual ambos os eletrões na ligação são contribuídos por um dador (base de Lewis) para um aceitador de eletrões (ácido de Lewis). O ácido de Lewis em complexos de coordenação, muitas vezes chamado de ião (ou átomo) metálico central, é o metal de transição ou metal de transição interna. As bases de Lewis dadoras, chamadas ligandos, podem ser uma grande variedade de produtos químicos—átomos, moléculas, ou iões. O único requisito é que eles tenham um ou mais pares de eletrões, que podem ser doados ao metal central. Mais frequentemente, isto envolve um átomo dador com um par solitário de eletrões que pode formar uma ligação coordenada com o metal. A esfera de coordenação consiste no ião ou átomo de metal central mais os seus ligandos acoplados. Os parênteses em uma fórmula englobam a esfera de coordenação.
Os ligandos são monodentados, do Grego para “com um dente”, quando se ligam ao metal central através de apenas um átomo. Aqui, o número de ligandos e o número de coordenação são iguais. Os ligandos com um átomo dador, como NH3, Cl−, e H2O, são ligandos monodentados. Muitos outros ligandos coordenam-se com o metal de formas mais complexas.
Ligandos bidentados são aqueles em que dois átomos se coordenam com o centro de metal. Por exemplo, a etilenodiamina (en, H2NCH2CH2NH2) contém dois átomos de nitrogénio, cada um deles com um par solitário e pode servir como uma base de Lewis (Figura 1a). Ambos os átomos podem coordenar para um único centro de metal. No complexo [Co(en)3]3+, existem três ligandos en bidentados, e o número de coordenação do ião cobalto(III) é seis (Figura 1b). Os números de coordenação mais comuns são dois, quatro, e seis, mas exemplos de todos os números de coordenação de 1 a 15 são conhecidos.
<img alt="Image1" src="/files/ftp_upload/11456/11456_Image_1.svg" style="text-align: center; height: 200px;" />
Figura 1. (a) A etilenodiamina (en) contém dois átomos de nitrogénio, cada um com um par solitário, que podem ser coordenados com um ião metálico. (b) Três ligandos en bidentados coordenam-se com um único ião cobalto.
Qualquer ligando que se liga a um ião central de metal por mais de um átomo dador é um ligando polidentado (“muitos dentes”) porque pode dentar o centro de metal com mais de uma ligação. O termo quelato do Grego para “garra” também é usado para descrever este tipo de interação. Muitos ligandos polidentados são ligandos quelantes, e um complexo que consiste em um ou mais destes ligandos e um metal central é um quelato. Um ligando quelante também é conhecido como agente quelante. Um ligando quelante segura o ião metálico de forma semelhante a uma garra de caranguejo a segurar um berlinde. Os ligandos polidentados são às vezes identificados com prefixos que indicam o número de átomos dadores no ligando. O complexo heme na hemoglobina é outro exemplo importante (Figura 2). Ele contém um ligando polidentado com quatro átomos dadores que se coordenam com o ferro.
<img alt="Image2" src="/files/ftp_upload/11456/11456_Image2.svg" style="text-align: center; height: 200px;" />
Figura 2:  O ligando único heme contém quatro átomos de nitrogénio que se coordenam com o ferro na hemoglobina para formar um quelato.
Este texto é adaptado de <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>.

Ligações Metal-Ligando

A hemoglobina no sangue, a clorofila nas plantas verdes, a vitamina B-12 e o catalisador usado na fabricação de polietileno contêm ...

Education

JoVE Core

Chemistry

Química

Transition Metals and Coordination Complexes

Metais de Transição e Complexos de Coordenação

transition-metals-and-coordination-complexes

KEY TERMS AND CONCEPTS

TERMOS-CHAVE E CONCEITOS

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

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Coordination Complexes and Chelation

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