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

В комплексном ионе ион металла связан с анионными или нейтральными молекулами, известными как лиганды. Лиганды имеют одну или несколько неподеленных пар электронов и действуют как доноры электронных пар или основания Льюиса. Они отдают электронную пару иону металла, который действует как акцептор электронной пары или кислота Льюиса.Таким образом, координированная ковалентная связь между ионом металла и лигандом образует аддукт кислоты и основания Льюиса. Отдающий электронную пару атом лиганда известен как донорный атом. Число окружающих ион металла донорных атомов коррелирует с координационным числом иона металла.В зависимости от количества присутствующих донорных атомов лиганды дополнительно классифицируются как монодентатные, бидентатные или полидентатные лиганды, которые могут быть заряженными или нейтральными. Монодентатные лиганды имеют только один донорный атом. Кислород донорный атом в нейтральной молекуле воды;азот является донорным атомом в заряженном цианид-ионе.Бидентатные лиганды имеют два донорных атома, находящиеся достаточно далеко друг от друга, чтобы одновременно связываться с ионом металла. Атомы азота трех молекул бипиридина связываются с ионом рутения с координационным числом шесть. Полидентатный лиганд имеет в своей структуре два или более донорских атомов.Здесь шесть атомов азота из двух молекул диэтилентриамина связываются с ионом кобальта. Поскольку несколько донорных атомов удерживают центральный ион металла подобно когтю, бидентатные и полидентатные лиганды также называются хелатирующими агентами. Хелатирующий агент имеет большее сродство к центральному иону металла, чем монодентатный лиганд, образуя более стабильный координационный комплекс.Это известно как хелатирующий эффект. Хелатирующие агенты универсальны. Они используются для комплексного связывания ионов металлов в реакции для увеличения срока хранения пищевых продуктов за счет образования комплексов с ионами металлов, участвующих в катализе реакций разложения, или для лечения отравления свинцом с помощью этилендиаминтетраацетата или ЭДТА.Образование комплексного иона влияет на физико-химические свойства иона металла и лигандов, например, изменение окислительно-восстановительного потенциала или цвета. Кроме того, лиганды могут вступать в такие реакции, как депротонирование гидратированных ионов металла или замещение другим сильно связанным лигандом. Здесь молекула воды заменена аммиаком, который сильнее связывается с ионом металла.

Связи металл-лиганд

Гемоглобин в крови, хлорофилл в зеленых растениях, витамин B-12 и катализатор, используемый при производстве полиэтилена, содержат координационные соединения. Ионы металлов, особенно переходных металлов, скорее всего образуют комплексы. 
 В этих комплексах переходные металлы образуют координатные ковалентные связи, своего рода взаимодействие Льюиса кислотно-основная, в котором оба электрона в связи вносят донор (Lewis основание) в акцептор электронов (Льюис-кислота). Кислота Льюиса в координационных комплексах, часто называемая центральным ионом металла (или атомом), является переходным металлом или внутренним переходным металлом. Доноры Lewis основание, называемые лигандами, могут быть самыми разными химикатами – атомами, молекулами или ионами. Единственным требованием является то, что у них есть одна или несколько электронных пар, которые могут быть переданы центральному металлу. Чаще всего это связано с атомом донора с одинокой парой электронов, которые могут сформировать координатную связь с металлом. Сфера координации состоит из центрального иона металла или атома плюс присоединенные лиганды. Скобки в формуле заключают сферу координации; виды за пределами скобок не являются частью сферы координации. 
 Лиганды однопутные, от греческих для “однозубый”, когда они соединяются с центральным металлом только через один атом. Здесь количество лигандов и номер координации равны. Лиганды с одним атомом донора, такие как NH3, CL- и H2O, являются однодогенными лигандами. Многие другие лиганды координируют с металлом в более сложной моде. 
 Лиганды бидентата — это лиганды, в которых два атома координируют центр металла. Например, этилендиамин (en, H2NCH2CH2NH2) содержит два атома азота, каждый из которых имеет одиноную пару и может служить в качестве основание Льюиса (рис. 1a). Оба атома могут координировать свою работу с одним центром металла. В комплексе [Co(en)3]3+ имеется три лиганда бидентата, а координационный номер иона кобальта(III) — шесть (рис. 1b). Наиболее распространенными номерами координации являются два, четыре и шесть, но известны примеры всех номеров координации от 1 до 15. 
 <img alt="Image1" src="/files/ftp_upload/11456/11456_Image_1.svg" style="text-align: center; height: 200px;" />
 Рисунок 1. (a) этилендиамин (en) содержит два атома азота, каждая из которых имеет одну пару, которые могут координировать с ионом металла. (b) три бидентата у лигандов координируют с одним кобальтовым ионом. 
 Любой лиганд, связывающий центральный ион металла более чем с одним атомом донора, является полидентационной лигандом (или “много зубов”), потому что он может укусить в металлический центр более чем одной связью. Термин хелат из греческого для «когота» также используется для описания этого типа взаимодействия. Многие полидентационные лиганды являются хелатными лигандами, а комплекс, состоящий из одной или нескольких из этих лигандов и центрального металла, является хелатом. Хелатинг лиганд также известен как хелатинг-агент. Хелатая лиганда держит металлический ион, скорее, как кобель краба, будет удерживать мрамор. Лиганды Polydentate иногда идентифицируются с префиксами, указывающими количество атомов донора в лигандах. Еще одним важным примером является гемный комплекс гемоглобина (рис. 2). Он содержит полидентат лиганд с четырьмя атомами донора, которые координируют железо. 
 <img alt="Image2" src="/files/ftp_upload/11456/11456_Image2.svg" style="text-align: center; height: 200px;" />
 Рисунок 2: Одинарная лиганда гема содержит четыре атома азота, которые координируют железо в гемоглобине, образуя хелат. 
 Этот текст адаптирован из<a href="https://openstax.org/books/chemistry-2e/pages/19-2-coordination-chemistry-of-transition-metals"> Openstax, Химия 2е изд., Chapter 19.2 Coordination Chemistry of Transition Metals</a>.

Гемоглобин в крови, хлорофилл в зеленых растениях, витамин B12 и катализатор, используемый при производстве полиэтилена, содержат ...

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Один

Transition Metals and Coordination Complexes

Переходные металлы и координационные комплексы

transition-metals-and-coordination-complexes

KEY TERMS AND CONCEPTS

ОСНОВНЫЕ ТЕРМИНЫ И ПОНЯТИЯ

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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Chemical Stoichiometry and Gases: Using Ideal Gas Law to Determine Moles

Chemical stoichiometry describes the quantitative relationships between reactants and products in chemical reactions.

In addition to measuring quantities ...

Analyze data to support the claim that the combined gas law describes the relationships among volume, pressure, and temperature for a sample of an ideal gas.

HS-PS1-9.

Coordination Complexes and Chelation

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