STRUCTURES AND ISOMERS

Coordination Chemistry
TRAN BUU DANG
HOCHIMINH CITY UNIVERSITY OF EDUCATION

Gary L.Miessler, Inorg Chem 5th ed, Pearson Education, 2014, chapter 9.
Housecroft, Sharpe, Inorg Chem 3rd ed, Pearson Education, 2008, chapter 20.
 Coordination compound vs organometallic compound
Phức chất nói chung
Coordination compounds are
composed of a metal atom or
ion and one or more ligands
(atoms, ions, or molecules)
that donate electrons to the
metal.

Phức cơ kim
Organometallic compounds
contain metal–carbon bonds
 Compositions

Center ion

3 3
Ligands Counterions (Anions)
Cầu ngoại
3 3

Cation = complex ion = coordination sphere

Cầu nội
 Dissociation in aqueous solvent
Sự điện li của cầu nội và cầu ngoại là điện li mạnh
NH3 NH3

H3N NH3 H3N NH3

Co - Co -

H3N NH3 H3N NH3

NH3 NH3

Sự điện li của các thành phần trong cầu nội là điện li yếu

NH3 NH3
H3N NH3 NH3
Co H3N Co
H3N NH3 3
NH3
NH3 NH3
Điện tích phức càng lớn --> Hòa tan trong nước càng nhiều
Tính chất ưa nước/kị nước của phối tử cũng ảnh hưởng độ tan
Các cách xác định số ion Cl- ở cầu ngoại: đo độ dẫn điện dd, pp chuẩn độ, pp phổ
Nomenclature
Nằm trong cầu nội: ide --> o
Nomenclature
Nomenclature
Nomenclature
Nomenclature
 Nomenclature Rules

1. The cation comes first, followed by the anion.

2. The ligands within the coordination sphere are written before the metal in the formula name.

3. The number of ligands of each kind is indicated by prefixes (in margin). In simple
cases, the prefixes in the second column are used. If the ligand name already includes these prefixes or
is complicated, it is set off in parentheses, and prefixes in the third column (ending in –is) are used.

4. Ligands are generally written in alphabetical order—according to the ligand name, not
the prefix.

5. The calculated oxidation number of the metal is put as a Roman numeral in parentheses after the
metal name. If the charge is negative, the suffix -ate is added to the name.
 Nomenclature Rules
[Co(NH3)6]Cl3: hexaamminecobalt(III) chloride
[Ni(NH3)2(H2O)2Cl]Br:
diamminediaquachloronickel(II) bromide

mercury (Hg) --> mercurate

copper (Cu) --> cuprate
phức chất tạo vòng
[Fe(CO)5]:pentacacbonyliron(0)
K4[Fe(CN)6]: potassium hexacyanoferrate(II)
 Nomenclature Rules

tetrachloroplatinate(II) [PtCl4]2-
hexachloroplatinate(IV) [PtCl6]2-
tetrachloroferrate(III) [FeCl4]-
dicyanoaurate(I) [Au(CN)2]-

cis- and trans-diamminedichloroplatinum(II)

μ-amido-μ-hydroxobis(tetramminecobalt(III))
Nomenclature Rules
 Coordination number: 2 and 3

[Au{P(cyclo-C6H11)3}]+ [AgTe7}]+ [Fe{N(SiMe2}3]+

 Coordination number: 4 and 5

[Ru(PMe2Ph)4}]+ [Zn{N(CH2CH2NH2)3}Cl]+ [Cu(bipy){N(CH2COO)2}3]+

 Coordination number: 6

[WMe6]+ [Re(S2C2Ph2)3]+
 Coordination number: 7

[TaCl4(PMe3)3] [ZrF7]3- [ScCl2(15-crown-5)]+

Coordination number: 8
 Isomerism
Isomerism
The same formula, different chemical properties

đồng phân cấu trúc đồng phân lập thể

Structural Isomerism Stereoisomerism
hydrate ion hóa
hóa Hydrate Ionization Geometric Optical
isomers isomers isomers isomers

hình học quang học

Coordination Linkage
isomers isomers

phối trí liên kết

 Isomerism

. H2O

Ionization isomers: Compounds with the same formula, but

which give different ions upon dissociation.
 Isomerism

Hydrate isomerism requires water to play two roles, as (1) a ligand and
as (2) an additional occupant (or solvate) within the crystal structure.
 Isomerism
2 kim loại
Coordination isomerism: Historically, a complete series of coordination isomers
required at least two metals. The ligand : metal ratio remains the same, but the
ligands attached to a specific metal ion change.
IV II

đp phối trí

Coordination isomers can also be composed of different metal ions, or the same
metal in different oxidation states:
 Isomerism
Coordination isomerism: the design of multidentate ligands that can bind to metals
in different way. kiểu liên kết khác nhau

bis(1-pyrazolylmethyl)ethylamine đp phối trí

 Isomerism
Linkage (Ambidentate) Isomerism:
ligands can bond to the metal through different atoms.
nguyên tử liên kết khác nhau

đp liên kết
 Stereoisomerism
Stereoisomers have the same ligands, but differ in their geometric arrangement.
 Stereoisomerism
Stereoisomers have the same ligands, but differ in their geometric arrangement.

The trans‐ and cis‐isomers of 
the square planar complex 
can be distinguished by IR 
spectroscopy
Stereoisomerism
Stereoisomerism
 Stereoisomerism – chiral complexes
A molecule is chiral only if it has no rotation-reflection (Sn) axes.
chiral molecules either have no symmetry elements (except identity, C1) or have only
axes of proper rotation (Cn).
 Stereoisomerism

1 1
1

4 4 5 6 3
5
6
3 6 5 4
3
2
2 2