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

In een complex ion is het metaalion gebonden aan anionische of neutrale moleculen, ook wel liganden genoemd. Liganden hebben een of meer vrije elektronenparen en fungeren als donoren van elektronenparen of Lewis-basen. Ze doneren het elektronenpaar aan het metaalion, die fungeert als een elektronenpaaracceptor of een Lewis-zuur.Dus een gecoördineerde covalente binding tussen het metaalion en ligand vormt een Lewis-zuur-base-adduct. Het ligandatoom dat een elektronenpaar doneert staat bekend als het donoratoom. Het aantal donoratomen rond het metaalion correleert met het coördinatiegetal van het metaalion.Afhankelijk van het aantal aanwezige donoratomen, worden liganden verder geclassificeerd als monodentate, bidentate of polydetate liganden, die geladen of neutraal kunnen zijn. Monodentate liganden hebben slechts één donoratoom. Zuurstof is een donoratoom in een neutraal watermolecuul;stikstof is een donoratoom in een geladen cyanide-ion.Bidentate liganden hebben twee donoratomen die voldoende ver van elkaar verwijderd zijn om gelijktijdig aan een metaalion te binden. De stikstofatomen van drie bipyridinemoleculen binden aan een rutheniumion met coördinatiegetal zes. Een polydentate ligand heeft twee of meer donoratomen in zijn structuur.Hier binden zes stikstofatomen uit twee moleculen diethyleentriamine zich aan een kobaltion. Aangezien meerdere donoratomen het centrale metaalion als een klauw lijken vast te houden, worden de bidentate en polydentate liganden ook wel chelaatvormers genoemd. Een chelaatvormer heeft meer affiniteit voor het centrale metaalion dan een monodentaat ligand en vormt een stabieler coördinatiecomplex.Dit staat bekend als het chelerende effect. Chelaatvormers zijn veelzijdig. Ze worden gebruikt om storende metaalionen in een reactie te complexeren om de houdbaarheid van voedselproducten te verlengen door sporenmetaalionen die betrokken zijn bij het katalyseren van ontledingsreacties te complexeren of door loodvergiftiging te behandelen met ethyleendiaminetetraacetaat of EDTA.De vorming van complexe ionen beïnvloedt de fysisch-chemische eigenschappen van de metaalionen en liganden, zoals verandering in oxidatie-en reductiepotentialen of kleuren. Bovendien kunnen liganden reacties ondergaan zoals deprotonering van gehydrateerde metaalionen of verplaatsing door een ander sterk aangetrokken ligand. Hier wordt het watermolecuul vervangen door ammoniak, dat zich sterker bindt aan het metaalion.

metaal-ligand-obligaties

De hemoglobine in het bloed, het chlorofyl in groene planten, vitamine B12 en de katalysator die wordt gebruikt bij de vervaardiging van polyethyleen bevatten allemaal coördinatieverbindingen. Ionen van de metalen, vooral de overgangsmetalen, vormen waarschijnlijk complexen. In deze complexen vormen overgangsmetalen gecoördineerde covalente bindingen, een soort Lewis-zuur-base-interactie waarbij beide elektronen in de binding door een donor (Lewis-base) worden bijgedragen aan een elektronenacceptor (Lewis-zuur). Het Lewis-zuur in coördinatiecomplexen, vaak een centraal metaalion (of atoom) genoemd, is het overgangsmetaal of het binnenste overgangsmetaal. De Lewis-basedonoren, liganden genoemd, kunnen een grote verscheidenheid aan chemicaliën zijn: atomen, moleculen of ionen. De enige vereiste is dat ze een of meer elektronenparen hebben, die aan het centrale metaal kunnen worden gedoneerd. Meestal gaat het hierbij om een donoratoom met een eenzaam elektronenpaar dat een gecoördineerde binding met het metaal kan vormen. De coördinatiesfeer bestaat uit het centrale metaalion of atoom plus de daaraan verbonden liganden. Haakjes in een formule omsluiten de coördinatiesfeer; soorten buiten de haakjes maken geen deel uit van de coördinatiesfeer. Liganden zijn monodentaat, van het Grieks voor ‘één tand’, wanneer ze via slechts één atoom verbinding maken met het centrale metaal. Hier zijn het aantal liganden en het coördinatiegetal gelijk. Liganden met één donoratoom, zoals NH3, Cl− en H2O, zijn monodentaatliganden. Veel andere liganden coördineren op complexere manieren met het metaal. Bidentate liganden zijn liganden waarin twee atomen coördineren met het metaalcentrum. Ethyleendiamine (en, H2NCH2CH2NH2) bevat bijvoorbeeld twee stikstofatomen, die elk een vrij paar hebben en kunnen dienen als een Lewis-base (Figuur 1a). Beide atomen kunnen coördineren met een enkel metaalcentrum. In het complex [Co(en)3]3+ zijn er drie tweetandige en-liganden, en het coördinatiegetal van het kobalt(III)-ion is zes (Figuur 1b). De meest voorkomende coördinatiegetallen zijn twee, vier en zes, maar er zijn voorbeelden bekend van alle coördinatiegetallen van 1 tot en met 15. <img alt="Image1" src="/files/ftp_upload/11456/11456_Image_1.svg" style="text-align: center; height: 200px;"> Figuur 1. (a) ethyleendiamine (en) bevat twee stikstofatomen, met elk een vrij paar, dat kan coördineren met een metaalion. (b) Drie tweetandige en-liganden coördineren met een enkel kobaltion. Elk ligand dat zich met meer dan één donoratoom aan een centraal metaalion bindt, is een polydentaatligand (of ‘veel tanden’), omdat het met meer dan één binding in het metaalcentrum kan bijten. De term chelaat uit het Grieks voor ‘klauw’ wordt ook gebruikt om dit soort interactie te beschrijven. Veel polydentaatliganden zijn chelaatvormende liganden, en een complex bestaande uit een of meer van deze liganden en een centraal metaal is een chelaat. Een chelerend ligand is ook bekend als een chelerend middel. Een chelaatvormende ligand houdt het metaalion vast, net zoals de klauw van een krab een knikker vasthoudt. Polydentate liganden worden soms geïdentificeerd met voorvoegsels die het aantal donoratomen in het ligand aangeven. Het heemcomplex in hemoglobine is een ander belangrijk voorbeeld (Figuur 2). Het bevat een polydentaat ligand met vier donoratomen die coördineren met ijzer. <img alt="Image2" src="/files/ftp_upload/11456/11456_Image2.svg" style="text-align: center; height: 200px;"> Figuur 2: Het enkele ligand-heem bevat vier stikstofatomen die samenwerken met ijzer in hemoglobine om een chelaat te vormen.

Metaal-ligand-obligaties

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain ...

Education

JoVE Core

Chemistry

Scheikunde

Eén

Transition Metals and Coordination Complexes

Overgangsmetalen en coördinatiecomplexen

transition-metals-and-coordination-complexes

KEY TERMS AND CONCEPTS

BELANGRIJKE TERMEN EN CONCEPTEN

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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