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

W żynie złożonym jon metalu jest związany z anionowymi lub obojętnymi cząsteczkami, znanymi jako ligandy. Ligandy mają jedną lub więcej samotnych par elektronów i działają jako donory par elektronów lub zasady Lewisa. Przekazują parę elektronów jonowi metalu, który działa jako akceptor par elektronów lub kwas Lewisa. W ten sposób koordynacyjne wiązanie kowalencyjne między jonem metalu a ligandem tworzy addukt kwasowo-zasadowy Lewisa.
Atom liganda oddający parę elektronów jest znany jako atom donorowy. Liczba atomów donorowych otaczających jon metalu koreluje z liczbą koordynacyjną jonu metalu.
W zależności od liczby obecnych atomów donorowych, ligandy są dalej klasyfikowane jako ligandy jednozębne, dwuzębne lub wielozębne, które mogą być naładowane lub obojętne.
Ligandy jednozębne mają tylko jeden atom donora. Tlen jest atomem donorowym w obojętnej cząsteczce wody; Azot jest atomem donorowym w naładowanym jonie cyjanku.
Ligandy Bidentate mają dwa atomy donorowe, które są wystarczająco daleko od siebie, aby jednocześnie związać się z jonem metalu. Atomy azotu trzech cząsteczek bipirydyny wiążą się z jonem rutenu o liczbie koordynacyjnej sześć.
Ligand wielozębny ma w swojej strukturze dwa lub więcej atomów donorowych. Tutaj sześć azotów z dwóch cząsteczek dietylenotriaminy wiąże się z jonem kobaltu.
Ponieważ wiele atomów donorowych wydaje się utrzymywać centralny jon metalu jak pazur, ligandy dwuzębne i wielozębne są również nazywane czynnikami chelatującymi.
Czynnik chelatujący ma większe powinowactwo do centralnego jonu metalu niż ligand jednozębny, tworząc bardziej stabilny kompleks koordynacyjny. Jest to tak zwany efekt chelatacji.
Środki chelatujące mają wszechstronne zastosowanie. Stosuje się je do kompleksowania interferujących jonów metali w reakcji - w celu wydłużenia okresu przydatności do spożycia produktów spożywczych poprzez kompleksowanie jonów metali śladowych biorących udział w katalizowaniu reakcji rozkładu lub leczeniu zatrucia ołowiem za pomocą etylenodiaminotetraoctanu lub EDTA.
Tworzenie jonów złożonych wpływa na właściwości fizykochemiczne jonów metalu i ligandów, takie jak zmiana potencjałów utleniania i redukcji lub kolorów. Ponadto ligandy mogą ulegać reakcjom, takim jak deprotonacja uwodnionych jonów metali lub wypieranie przez inny silnie przyciągany ligand. Tutaj cząsteczka wody jest zastępowana przez amoniak, który silniej wiąże się z jonem metalu.

wiązania metal-ligand

Hemoglobina we krwi, chlorofil w roślinach zielonych, witamina B12 i katalizator stosowany w produkcji polietylenu zawierają związki koordynacyjne. Jony metali, zwłaszcza metali przejściowych, prawdopodobnie tworzą kompleksy.

W tych kompleksach metale przejściowe tworzą koordynacyjne wiązania kowalencyjne, rodzaj interakcji kwas Lewisa z zasadą, w której oba elektrony w wiązaniu są przekazywane przez donora (zasadę Lewisa) do akceptora elektronów (kwas Lewisa). Kwas Lewisa w kompleksach koordynacyjnych, często nazywany centralnym jonem metalu (lub atomem), jest metalem przejściowym lub wewnętrznym metalem przejściowym. Donorami zasady Lewisa, zwanymi ligandami, może być wiele różnych substancji chemicznych — atomy, cząsteczki lub jony. Jedynym warunkiem jest to, żeby miały jedną lub więcej par elektronów, które mogą zostać oddane metalowi centralnemu. Najczęściej dotyczy to atomu dawcy z samotną parą elektronów, które mogą tworzyć wiązanie koordynacyjne z metalem. Sfera koordynacyjna składa się z centralnego jonu lub atomu metalu oraz przyłączonych do niego ligandów. Nawiasy we wzorze obejmują sferę koordynacyjną; gatunki poza nawiasami nie są częścią sfery koordynacyjnej.

Ligandy są jednokleszczowe (co z greckiego oznacza „jednozębny”), gdy łączą się z metalem centralnym tylko przez jeden atom. Tutaj liczba ligandów i liczba koordynacyjna są równe. Ligandy z jednym atomem donora, takie jak NH3, Cl- i H2O, są ligandami jednokleszczowymi. Wiele innych ligandów koordynuje się z metalem w bardziej złożony sposób.

Ligandy dwukleszczowe to takie, w których dwa atomy koordynują się z metalowym centrum. Na przykład etylenodiamina (en, H2NCH2CH2NH2) zawiera dwa atomy azotu, z których każdy ma samotną parę i może służyć jako zasada Lewisa (Rysunek 1a). Oba atomy mogą koordynować się z jednym metalowym centrum. W kompleksie [Co(en)3]3+ występują trzy dwukleszczowe ligandy en, a liczba koordynacyjna jonu kobaltu(III) wynosi sześć (Rysunek 1b). Najpopularniejszymi liczbami koordynacyjnymi są dwa, cztery i sześć, ale znane są przykłady wszystkich liczb koordynacyjnych od 1 do 15.

<img alt="Image1" src="/files/ftp_upload/11456/11456_Image_1.svg" style="text-align: center; height: 200px;" />

Rysunek 1. (a) etylenodiamina (en) zawiera dwa atomy azotu, każdy z pojedynczą parą, które mogą koordynować z jonem metalu. (b) Trzy dwukleszczowe ligandy koordynują się z pojedynczym jonem kobaltu.

Każdy ligand, który wiąże się z centralnym jonem metalu przez więcej niż jeden atom dawcy, jest ligandem wielokleszczowym (lub „wieloma zębami”), ponieważ może wgryźć się w środek metalu za pomocą więcej niż jednego wiązania. Do opisania tego typu interakcji używa się również terminu chelat z języka greckiego oznaczającego „pazur”. Wiele ligandów wielokleszczowych to ligandy chelatujące, a kompleks składający się z jednego lub większej liczby tych ligandów i metalu centralnego jest chelatem. Ligand chelatujący jest również znany jako środek chelatujący. Ligand chelatujący utrzymuje jon metalu w podobny sposób, w jaki pazur kraba utrzymuje marmur. Ligandy wielokleszczowe są czasami identyfikowane za pomocą przedrostków wskazujących liczbę atomów dawcy w ligandzie. Kolejnym ważnym przykładem jest kompleks hemowy w hemoglobinie (ryc. 2). Zawiera ligand wielokleszczowy z czterema atomami dawcy, które koordynują się z żelazem.

<img alt="Image2" src="/files/ftp_upload/11456/11456_Image2.svg" style="text-align: center; height: 200px;" />

Rysunek 2: Hem pojedynczego liganda zawiera cztery atomy azotu, które koordynują się z żelazem w hemoglobinie, tworząc chelat.

Wiązania metal-ligand

Hemoglobina we krwi, chlorofil w zielonych roślinach, witamina B12 i katalizator używany do produkcji polietylenu zawierają ...

Education

JoVE Core

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Transition Metals and Coordination Complexes

Metale przejściowe i kompleksy koordynacyjne

transition-metals-and-coordination-complexes

KEY TERMS AND CONCEPTS

Kluczowe terminy i pojęcia

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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