Name: transition metal shapes from coordination number
Uploaded: 2020-09-24T15:06:53.000Z
Duration: 2 min 57 s
Channel: JoVE

K12 Standards

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New York State Science Learning Standards

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Physical Science

HS. Structure and Properties of Matter

HS-PS2-6.

Coordination Number and Geometry

Veel overgangsmetalen vertonen meerdere oxidatiegetallen die bijdragen aan hun unieke eigenschappen, zoals kleuren. Maar hoe wordt het oxidatiegetal van het metaal bepaald? Coördinatieverbindingen zijn elektrisch neutrale soorten die bestaan uit een coördinatiecomplex en tegenionen met een primaire en secundaire valentie.De primaire valentie is het oxidatiegetal van het metaalion. Om het oxidatiegetal te vinden, begint u met het identificeren van de ladingen die worden bijgedragen door de liganden en tegenionen. Tel vervolgens de ladingen op en bepaal het oxidatiegetal van het metaalion.Als alle liganden neutraal zijn, wordt de lading van het complexe ion het oxidatiegetal van het metaalion. De secundaire valentie verwijst naar het aantal liganden dat rechtstreeks aan het centrale metaalion is gebonden, ook wel het coördinatiegetal genoemd. Hier is het coördinatiegetal van rhodium zes.Sommige metaalionen hebben slechts één coördinatiegetal. Kobalt(III)en platina(II)hebben een coördinatiegetal van 6 en 4. Voor veel metaalionen varieert het coördinatiegetal echter van 2 tot 6.De relatieve grootte van liganden en metaalionen beïnvloedt het coördinatiegetal. Zo coördineren kleinere liganden zoals fluor zes keer met ijzer(III)vergeleken met het grotere chloor, dat slechts vier keer coördineert. Negatieve ladingen die door liganden aan het metaalion worden verleend, beïnvloeden ook het coördinatiegetal.Het coördinatiegetal van nikkel(II)met neutrale watermoleculen is 6, dat wordt teruggebracht tot 4 met anionische chloride-ionen. De geometrische vorm van het complexe ion hangt gedeeltelijk af van het coördinatiegetal van een metaalion. Een complex met een coördinatiegetal van twee heeft een lineaire geometrie, waarbij twee liganden 180°uit elkaar staan aan weerszijden van het metaalion.Een complex met een coördinatiegetal 4 vertoont twee soorten geometrie op basis van het valentie-elektron in de d-subshell. Metaalionen met acht d-elektronen, zoals palladium(II)zijn vierkant vlak. Terwijl metaalionen met tien d-elektronen, zoals zink(II)een tetraëdrische geometrie vertonen.Een complex met een coördinatiegetal 6 is octaëdrisch. De zes liganden bezetten zes hoekpunten, vier liganden vormen de hoeken van een vierkant en de overige twee de vlakken boven en onder op een equivalente afstand. Een octaëder verschijnt dus als twee piramides met een gemeenschappelijke vierkante basis en acht zijden.

coördinatiegetal en geometrie

Voor overgangsmetaalcomplexen bepaalt het coördinatiegetal de geometrie rond het centrale metaalion. Tabel 1 vergelijkt coördinatiegetallen met moleculaire geometrie. De meest voorkomende structuren van de complexen in coördinatieverbindingen zijn octaëdrische, tetraëdrische en vierkante vlakke structuren. <table style="margin-left: auto; margin-right: auto;"> <tbody> <tr> <td style="color: black; border: 1px solid black; text-align: center;"> Coordination Number </td> <td style="color: black; border: 1px solid black; text-align: center;">Molecular Geometry</td> <td style="color: black; border: 1px solid black; text-align: center;">Example</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">2</td> <td style="color: black; border: 1px solid black; text-align: center;">linear</td> <td style="color: black; border: 1px solid black; text-align: center;">   [Ag(NH3)2]+   </td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">3</td> <td style="color: black; border: 1px solid black; text-align: center;">trigonal planar</td> <td style="color: black; border: 1px solid black; text-align: center;">[Cu(CN)3]2−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">4</td> <td style="color: black; border: 1px solid black; text-align: center;">  tetrahedral(d0 or d10), low oxidation states for M </td> <td style="color: black; border: 1px solid black; text-align: center;">[Ni(CO)4]</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">4</td> <td style="color: black; border: 1px solid black; text-align: center;">square planar (d8)</td> <td style="color: black; border: 1px solid black; text-align: center;">[NiCl4]2−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">5</td> <td style="color: black; border: 1px solid black; text-align: center;">trigonal bipyramidal</td> <td style="color: black; border: 1px solid black; text-align: center;">[CoCl5]2−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">5</td> <td style="color: black; border: 1px solid black; text-align: center;">square pyramidal</td> <td style="color: black; border: 1px solid black; text-align: center;">[VO(CN)4]2−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">6</td> <td style="color: black; border: 1px solid black; text-align: center;">octahedral</td> <td style="color: black; border: 1px solid black; text-align: center;">[CoCl6]3−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">7</td> <td style="color: black; border: 1px solid black; text-align: center;">pentagonal bipyramid</td> <td style="color: black; border: 1px solid black; text-align: center;">[ZrF7]3−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">8</td> <td style="color: black; border: 1px solid black; text-align: center;">square antiprism</td> <td style="color: black; border: 1px solid black; text-align: center;">[ReF8]2−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">8</td> <td style="color: black; border: 1px solid black; text-align: center;">dodecahedron</td> <td style="color: black; border: 1px solid black; text-align: center;">[Mo(CN)8]4−</td> </tr> <tr> <td style="color: black; border: 1px solid black; text-align: center;">9 and above</td> <td style="color: black; border: 1px solid black; text-align: center;">more complicated structures</td> <td style="color: black; border: 1px solid black; text-align: center;">[ReH9]2−</td> </tr> </tbody> </table> Tabel 1. Coördinatiegetallen en moleculaire geometrie. In tegenstelling tot hoofdgroepatomen waarin zowel de bindende als niet-bindende elektronen de moleculaire vorm bepalen, veranderen de niet-bindende d-elektronen de rangschikking van de liganden niet. Octaëdrische complexen hebben een coördinatiegetal van zes, en de zes donoratomen zijn gerangschikt op de hoeken van een octaëder rond het centrale metaalion. Voorbeelden zijn te zien in Figuur 1. De chloride- en nitraatanionen in [Co(H2O)6]Cl2 en [Cr(en)3](NO3)3, en de kaliumkationen in K2[PtCl6] staan buiten de haakjes en zijn niet gebonden aan het metaalion. <img alt="Image1" src="/files/ftp_upload/11457/11457_Image_1.svg" style="text-align: center; height: 200px;"> Figuur 1. Veel overgangsmetaalcomplexen nemen octaëdrische geometrieën aan, waarbij zes donoratomen bindingshoeken van 90° vormen rond het centrale atoom met aangrenzende liganden. Merk op dat alleen liganden binnen de coördinatiesfeer de geometrie rond het metaalcentrum beïnvloeden. Voor overgangsmetalen met een coördinatiegetal van vier zijn twee verschillende geometrieën mogelijk: tetraëdrisch of vierkant vlak. In tetraëdrische complexen zoals [Zn(CN)4]2− (Figuur 3) vormt elk van de ligandparen een hoek van 109,5°. In vierkante vlakke complexen, zoals [Pt(NH3)2Cl2], heeft elk ligand twee andere liganden onder hoeken van 90° (de cis-posities genoemd) en één extra ligand onder een hoek van 180°, in de trans-positie. <img alt="Image2" src="/files/ftp_upload/11457/11457_Image_2.svg" style="text-align: center; height: 200px;"> Figuur 2. Overgangsmetalen met een coördinatiegetal van vier kunnen een tetraëdrische geometrie (a) aannemen zoals in K2[Zn(CN)4] of een vierkante vlakke geometrie (b) zoals weergegeven in [Pt(NH3)2Cl2].

Coördinatiegetal en geometrie

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to ...

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Transition Metals and Coordination Complexes

Overgangsmetalen en coördinatiecomplexen

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KEY TERMS AND CONCEPTS

BELANGRIJKE TERMEN EN CONCEPTEN

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 [Cu(CN)3]2−. Four-coordinate complexes can be tetrahedral for d0 or d10 metals and for metals in low oxidation states, as in [Ni(CO)4], or square planar for d8 metals, as in [NiCl4]2−.

A coordination number of 5 can lead to two shapes. These are trigonal bipyramidal, as in [CoCl5]2−, and square pyramidal, as in [VO(CN)4]2−. A coordination number of 6 gives an octahedral geometry, as in [CoCl6]3−. Higher coordination numbers can form more complex shapes, including a pentagonal bipyramid for 7, square antiprism and dodecahedron for 8, and more complicated structures for 9 and above.

Only ligands in the coordination sphere affect the geometry around the metal center. In octahedral complexes, six donor atoms sit at the corners of an octahedron and make 90° angles with adjacent ligands. Examples include [Co(H2O)6]Cl2, [Cr(en)3](NO3)3, and K2[PtCl6], where the ions outside the brackets are not bonded to the metal ion.

Unlike main group atoms, the nonbonding d electrons in transition metals do not change ligand arrangement. For coordination number 4, tetrahedral and square planar geometries are both possible. In tetrahedral complexes such as K2[Zn(CN)4], the ligand pairs form 109.5° angles. In square planar complexes such as [Pt(NH3)2Cl2], ligands have cis positions at 90° and a trans position at 180°.

Transition Metal Shapes from Coordination Number

transition-metal-shapes-from-coordination-number

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 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...

coordination number and geometry

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

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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

Learn how coordination number predicts the shapes of transition metal complexes, including linear, tetrahedral, square planar, octahedral, and other geometries.

Transition Metal Shapes from Coordination Number | JoVE K12

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Transition Metal Shapes from Coordination Number

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