Transition Metals & Coordination Compounds

Coordination Compounds

A coordinate covalent bond is a pair of electrons from a donor shared with an acceptor.

An example of a coordinate covalent bond is the one formed between ammonia and boron trifluoride.

Coordinate covalent bonds frequently are formed in Lewis acid-base reactions.

The boron of BF3 has an empty valence orbital which is able to accept the electron pair donated by NH3.
2

The ammine complexes contain NH3 molecules bonded to metal ions by coordinate covalent bonds, e.g., [Cu(NH3)4]2+. Dilute aqueous NH3 reacts with metal ions to form the insoluble metal hydroxides or hydrated oxides.
The exceptions to this trend are metals that form strong, water soluble hydroxides.
Group IA cations and the heavier Group IIA cations, Ca2+, Sr2+, and Ba2+.

Ammine Complexes
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Ammine Complexes

Cu and Fe both react with aqueous ammonia to form hydroxides.

Metal hydroxides dissolve in excess aqueous NH3 to form ammine complexes.

Properties of Coordination Compounds

The charge on a complex is the sum of its constituent charges (or oxidation states)
Determine the charge of the metal in
[Pt(NH3 )6 ]4+ [SnCl6 ]2 [Co(CO)5 NO2]SO4

Dot formula suggest coordination compounds

CrCl3 6H2O also means [CrCl2(OH2)4]Cl 2H2O PtCl4 6NH3 also means [Pt(NH3)6]Cl4

A ligand is a Lewis base that coordinates to a central metal atom or ion. A donor atom is the atom in a ligand that donate a lone pair of electrons to form a coordinate covalent bond. A unidentate ligand is a ligand that can bind through only one atom.

Important Terms
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Typical Neutral Unidentate Ligands

Ion/Molecule NH3 CO NO PH3 Name ammonia carbon monoxide nitrogen monoxide phosphine

Name as a Ligand
ammine carbonyl nitrosyl phosphine

Typical Anionic Unidentate Ligands

Ion/Molecule CNFNO2OHName cyanide fluoride nitrite hydroxide Name as a Ligand cyano fluoro nitro hydroxo
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A polydentate ligand is a ligand that can bind through more than one donor atom.
Bidentate oxalate (ox, C2O42-) , ethylenediamine (en) Tridentate diethylenetriamine (dien) hexadentate ethylenediamine tetraacetic acid (EDTA)

Chelate complexes are complexes that have a metal atom or ion and polydentate ligand(s) that form rings.

Important Terms
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The coordination number is the number of donor atoms coordinated to a metal atom or ion. A coordination sphere includes the metal atom or ion and the ligands coordinated to it. The coordination sphere does not include uncoordinated counter ions.

Important Terms
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Nomenclature
Rules for Naming Complex Species 1. Cations (+ ions) are named before anions (- ions).
2.

Ligands are named in alphabetical order.

Prefixes that specify the number of each kind of monodentate ligand (di = 2, tri = 3, tetra = 4, penta = 5, hexa = 6, etc.) are not used in alphabetizing Prefixes that are part of the name of the ligand, such as in diethylamine, are used to alphabetize the ligands.
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3.

For polydentate chelating ligands, these prefixes are used to specify the number of those ligands that are attached to the central atom.
bis = 2 tris = 3 tetrakis = 4 pentakis = 5 hexakis = 6

[Co(en)3]3+ - tris(ethylenediamine) NOT tri(ethylenediamine) [Co(en)2 Cl2 ]+ - dichlorobis(ethylenediamine) NOT dichlorobi(ethylenediamine)

Nomenclature
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4.

The names of most anionic ligands end in the suffix -o.

Examples of ligands ending in o are:
ClS2O2OHCNNO3SO42S2O32CNSchloro sulfido oxo hydroxo cyano nitrato sulfato thiosulfato thiocyanato

Nomenclature
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5.

The names of most neutral ligands are unchanged when used in naming the complex.
There are several important exceptions to this rule including:
NH3 H 2O CO NO ammine aqua carbonyl nitrosyl

Nomenclature
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6.

The oxidation number of a metal that exhibits variable oxidation states is designated by a Roman numeral in parentheses following the name of the complex ion or molecule. If a complex is an anion, the suffix "ate" ends the name.
No suffix is used in the case of a neutral or cationic complex. Usually, the English stem is used for a metal; the Latin stem is substituted for those in Latin.

7.

ferrate instead of ironate plumbate instead of leadate Argentate for Ag Stannate for Sn

Nomenclature

Name the following compounds: Na3[Fe(Cl)6] sodium hexachloroferrate (III) [Ni(NH3)4(OH2)2](NO3)2 tetraamminediaquanickel(II) nitrate

Nomenclature
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Write formulas for the following compounds: potassium hexacyanochromate(III) K3[Cr(CN)6]

tris(ethylenediammine) cobalt(III) nitrate [Co(en)3] (NO3)3

Nomenclature
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The structures of coordination compounds are controlled primarily by the coordination number of the metal. Usually the structures can be predicted by VSEPR theory

The geometries and hybridizations for common coordination numbers are summarized in this table.

Structures
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Structures
Coordination Number
2 4 Geometry linear tetrahedral

Metal Hybridization
sp sp3

Example Ag[NH3)2]+ [Zn(CN)4]2-

4
5

square planar
trigonal bipyramid Square pyramidal octahedral

dsp2 or sp2d
dsp3

[Ni(CN)4]2Fe(CO)5 [Ni(CN)5]3[Fe(CN)6]420

5
6

d2sp2
d2sp3 or sp3d2

Structure and Function

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Structural (Constitutional) Isomers Structural isomers involve different atom to ligand bonding sequences. Ionization or Ion-Ion Exchange Isomers
[Pt(NH3)4Cl2]Br2 compared to [Pt(NH3)4Br2]Cl2 Note where the Cls and Brs are in the structures, that is what makes these two species isomers.

Isomerism in Coordination Compounds

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[Pt(NH3)4Cl2]Br2 [Pt(NH3)4Br2]Cl2

Structural (Constitutional) Isomers

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Hydrate isomers (Solvation isomerism) are a special case of ionization isomers in which water molecules may be changed from inside to outside the coordination sphere. For example:

Note whether the water molecule(s) are inside or outside the coordination sphere.

[Cr(OH2)6]Cl3 vs. [Cr(OH2)5Cl]Cl2. H2O vs. [Cr(OH2)4Cl2]Cl2. 2H2O

Structural (Constitutional) Isomers

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[Cr(OH2)6]Cl3

[Cr(OH2)5Cl]Cl2. H2O

[Cr(OH2)4Cl2]Cl2. 2H2O

Structural (Constitutional) Isomers

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Coordination isomers denote an exchange of ligands between the coordination spheres of the cation and anion. For example look at these two isomers:

The isomeric distinction is whether the ligands are on the cation or the anion.

[Pt(NH3)4][PtCl6] vs [Pt(NH3)4Cl2][PtCl4]

Structural (Constitutional) Isomers

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[Pt(NH3)4][PtCl6]

[Pt(NH3)4Cl2][PtCl4] Structural (Constitutional) Isomers

Linkage isomers have ligands that bind to the metal in more than one way. For example:
cyano -CNnitro -NO2compared to compared to isocyano -NCnitrito -ONO-

Note which atom in the ligand is bound to the central metal atom.

[Co(NH3)5ONO]Cl2 vs. [Co(NH3)5NO2]Cl2

Structural (Constitutional) Isomers

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[Co(NH3)5ONO]Cl2

[Co(NH3)5NO2]Cl2

Structural (Constitutional) Isomers

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Stereoisomers are isomers that have different spatial arrangements of the atoms relative to the central atom. Complexes with only simple ligands can occur as stereoisomers only if they have coordination numbers equal to or greater than four.

Stereoisomers
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Geometrical or positional isomers are stereoisomers that are not optical isomers. Cis-trans isomers have the same kind of ligand either adjacent to each other (cis) or on the opposite side of the central metal atom from each other (trans). Note where the ligands are positioned relative to the central atom.

Stereoisomers
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cis- [Pt(NH3)2Cl2] trans-[Pt(NH3)2Cl2]

Stereoisomers
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Isomerism due to changes in spatial orientation is known as sterioisomerism Other types of isomerism can occur in octahedral complexes. Complexes of the type [MA2B2C2] can occur in several geometric isomeric forms:

trans- trans- trans cis- cis- cis cis- cis- trans-

Stereoisomers
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trans-diammine-trans-diaqua-transdichloroplatinum(IV) ion

Stereoisomers
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cis-diammine-cis-diaqua-cisdichloroplatinum(IV) ion

Stereoisomers
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trans-diammine-cis-diaqua-cisdichloroplatinum(IV) ion

Stereoisomers
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Stereoisomers
cis-diammine-trans-diaqua-cis-dichloroplatinum(IV) ion

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Mertriamminetrichlorocobalt (III)

Factriamminetrichlorocobalt (III)

Optical isomers are mirror images of each other that are not superimposable. The cis-diammine-cis-diaqua-cisdichlorocobalt(III) ion has two different forms called optical isomers or enantiomers.

Stereoisomers
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These are the optical isomers of: cis-diammine-cis-diaqua-cis-dichloroplatinum (IV) ion

Stereoisomers

Stereoisomers

Separate equimolar solutions of the two isomers rotate plane polarized light by equal angles but in opposite directions.
The phenomenon of rotation of polarized light is called optical activity.

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Delta cisdichlorobis(ethylenediamine)cobal t (III)

Lambda cisdichlorobis(ethylenediamine)cobal t (III)

Show all four isomers of [Co(NH3)3(NO2)3]. Determine the number and the types of isomers in

Draw the correct structure of

(i) dichlorobis(ethylenediamine)platinum (IV) chloride (ii) tris(ethylenediamine) chromium (III) Triaqua-cis-dibromochlorochromium (III) Optical isomers of cisdiamminebis(ethylenediamine)cobalt (III)

Compounds

of Transition metal complexes solution.

[Fe(H2O)6]3+

[Ni(H2O)6]2+

[Zn(H2O)6]2+

[Co(H2O)6]2+ [Cu(H2O)6]2+

Black & White

When a sample absorbs light, what we see is the sum of the remaining colors that strikes our eyes.

If a sample absorbs all wavelength of visible light, none reaches our eyes from that sample. Consequently, it appears black.

If the sample absorbs no visible light, it is white or colorless.

Absorption and Reflection

If the sample absorbs all but orange, the sample appears orange.

Further, we also perceive orange color when visible light of all colors except blue strikes our eyes. In a complementary fashion, if the sample absorbed only orange, it would appear blue; blue and orange are said to be complementary colors.

Bonding in Coordination Compounds

Crystal Field Theory Crystal field theory provides a satisfactory explanation of the color and magnetic properties of coordination compounds.

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Crystal Field Theory

Crystal field theory treats the ligands as point charges and considers the effect of these point charges on the relative energies of the d orbitals.

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The five d orbitals can be divided into two subsets. The dz2 and dx2-y2 orbitals called the eg orbitals They are directed along the x, y, and z axes. The dxy, dxz, and dyz orbitals called the t2g orbitals These orbitals are directed between the x, y, and z axes.

In an octahedral coordination complex, the ligands approach the central metal along the x, y, and z axes.
There is a more repulsive environment for electrons in the eg orbitals (on x, y, and z axes) than for electrons in the t2g orbitals (in between the axes).

An electric field (provided by the crystal field) splits the degeneracy of the five d orbitals into:
1. Two higher energy orbitals (eg) 2. And three lower energy orbitals (t2g).

Crystal Field Theory

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Crystal Field Theory

The energy separation between the two sets of d orbitals is the crystal field splitting energy - oct. octahedral is proportional to the crystal field strength of the ligands.

Color and the Spectrochemical Series

The spectrochemical series reflects the ligand arrangement given on the previous slide.
Ligand field strength is proportional to the crystal field splitting. Strong field ligands cause large crystal field splitting Consequently, more energetic radiation needed to excite electron Weak field ligands cause small crystal field splitting Less energetic radiation needed to excite electron

Weak field, absorbs low energy radiation eg. RED

Strong filed, high energy radiation eg. Violet

 Strong field ligands cause large crystal field splitting, which lead to low spin complexes (more diamagnetic) Weak field ligands cause small crystal field splitting, which lead to high spin complexes (more paramagnetic)

Magnetic Properties and Spectrochemical Series

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Octahedral, Tetrahedral & Square Planar

CF

Splitting pattern for various molecular geometry

dx2-y2dz2
Octahedral
M

dx2-y2
Tetrahedral dxy
M

dyz dxz

Square planar
M

dxy

dz2 dxy dyz dxz dx2-y2dz2

Small High Spin

dx dyz
Mostly d8 (Majority Low spin) Strong field ligands i.e., Pd2+, Pt2+, Ir+, Au3+
z

Pairing energy Vs. Weak field < Pe Strong field > Pe

Name the compound K4[MnF6]. potassium hexafluoromanganate (II) What are its geometry, magnetic properties, and hybridization at Mn?

The 6 fluoride ions are in an octahedral geometry. There will be 5 unpaired electrons in a high spin complex. The Mn atom has sp3d2 hybrid orbitals.

Color and the Spectrochemical Series

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Name the compound [Mn(NH3)6]Cl2. manganese (II) hexaamminechloride What are its geometry, magnetic properties, and hybridization at Mn?

The 6 ammonia molecules are in an octahedral geometry. There will be 1 unpaired electron in a low spin complex The Mn atom is d2sp3 hybridized.

Color and the Spectrochemical Series

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