Part5: Transition Metal and
Coordination Chemistry
SORACHAI SAE-LIM
DEPARTMENT OF CHEMISTRY
MAHIDOL WITAYANUSORN SCHOOL
Website: www.mwit.ac.th/~teppode
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The elements in the Periodic Table which correspond to
the d-orbitals and f-orbitals
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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มีเลขออกซิเดชันได้หลายค่า
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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Complex
Mn2+
Mn3+
Mn4+ Mn6+
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Mn7+
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Central atom
Ligands
Counter ion
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A coordination complex consists of a central atom, usually
a metal ion, bound to a set of ligands by coordinate bonds.
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
ปัจจัยทีม่ ผี ลต่ อโครงสร้ างของสารประกอบ
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•Steric hindrance
Steric effect
•Electronic structure of metal
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Coordination number 1
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Coordination number 2
[Fe{NS2(Me)2Ph2)2}2]
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Coordination number 3
Trigonal planar structures are observed, and examples
involving d10 metal centre's include:
[Fe{N(SiMe3)2}3]
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
Coordination number 3
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Trigonal planar, the parent shape of three-coordination,
and the way it can transform to other known geometries.
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Coordination number 4
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Tetrahedral complexes
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Coordination number 4
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Square planar complexes are rarer than tetrahedral, and are
often associated with d8 configurations: e.g. [PdCl4]2-, [PtCl4]2-,
[AuCl4]-, [AuBr4]-
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Coordination number 5
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
Coordination number 6
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
Monodentate ligands
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Bidentate ligands
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
Tridentate ligands
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Tetradentate ligands
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จงบอกชนิดของ EDTA
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
จงบอกชนิดของ ligand ข้อ a-d
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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Naming Coordination Compounds
A. To name a coordination compound, no matter whether the
complex ion is the cation or the anion, always name the
cation before the anion. (This is just like naming an ionic
compound.)
NaCl
K4[Fe(CN)6]
Na+Cl-
Sodium chloride
potassium hexacyanoferrate(II)
Solution: potassium is the cation and the complex ion is the anion.
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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Naming Coordination Compounds
B. In
naming the complex ion:
1. Name the ligands first, in alphabetical order, then the metal atom
or ion.
Note: The metal atom or ion is written before the ligands in the
chemical formula.
[Cr(NH3)3(H2O)3]Cl3
Solution:
•The complex ion is inside the
parentheses, which is a cation.
•The ammine ligands are named before
the aqua ligands according to
alphabetical order.
triamminetriaquachromium (III) chloride
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
2. The names of some common ligands are
listed in Table 1.
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2.1For anionic ligands end in "-o"; for anions that end in
"-ide"(e.g. chloride),
"-ate" (e.g. sulfate, nitrate)
"-ite" (e.g. nirite)
change the endings as follows:
-ide
-o
-ate
-ato
-ite
-ito
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Table 1. Names of Some Common Ligands
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2.2For neutral ligands, the common name of the molecule is
used
H2NCH2CH2NH2
(ethylenediamine).
Important exceptions:
water
ammonia
carbon monoxide
N2
O2
is called
is called
is called
is called
is called
‘aqua’,
‘ammine’
‘carbonyl’
‘dinitrogen’
‘dioxygen’
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Table 2. Names of Some Common Ligands
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3. Greek prefixes are used to designate the number of each
type of ligand in the complex ion, e.g. di-, tri- and tetra-.
3.1 If the ligand already contains a Greek prefix (e.g. ethylenediamine)
3.2 If it is polydentate ligands (ie. can attach at more than one
binding site) the prefixes bis-, tris-, tetrakis-, pentakis-, are used instead.
The numerical prefixes are listed in Table 3
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4. After naming the ligands, name the central metal.
4.1 If the complex ion is a cation, the metal is named same as the element.
For example,
Co
Pt
cobalt
platinum.
4.2 If the complex ion is an anion,
The name of the metal ends with the suffix –ate.
For example,
Co
Pt
cobaltate
platinate
4.3 For some metals, the Latin names are used in the complex anions
For example
Fe is called ferrate (not ironate).
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Table 4: Name of Metals in Anionic Complexes
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5. Following the name of the metal, the oxidation state of
the metal in the complex is given as a Roman numeral in
parentheses.
Na2[NiCl4]
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sodium tetrachloronickelate(II)
C. To name a neutral complex molecule, follow the rules of
naming a complex cation. Remember: Name the (possibly
complex) cation BEFORE the (possibly complex) anion.
Pt(NH3)2Cl4
diamminetetrachloroplatinum(IV)
Solution: This is a neutral molecule because the charge on Pt+4
equals the negative charges on the four chloro ligands.
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
[Pt(NH3)5Cl]Br3
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Answer: pentaamminechloroplatinum(IV) bromide
Solution:
•The complex ion is a cation, the counter anion is the 3 bromides.
•The charge of the complex ion must be +3 since it bonds with 3
bromides.
•The NH3 are neutral molecules while the chloride carries - 1 charge.
Therefore, the oxidation number of platinum must be +4.
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
[Pt(H2NCH2CH2NH2)2Cl2]Cl2
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Answer:
dichlorobis(ethylenediamine)platinum(IV) chloride
Solution:
• ethylenediamine is a bidentate ligand, the bisprefix is used instead of di-
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
K4[Fe(CN)6]
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Answer:
potassium hexacyanoferrate(II)
Solution:
potassium is the cation and the complex ion is the anion.
Since there are 4 K+ binding with a complex ion, the charge on the
complex ion must be - 4.
Since each ligand carries –1 charge, the oxidation number of Fe
must be +2.
The common name of this compound is potassium ferrocyanide.
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
Can you give the molecular formulas of the following coordination
compounds?
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1. hexaammineiron(III) nitrate
2. ammonium tetrachlorocuprate(II)
3. sodium monochloropentacyanoferrate(III)
4. potassium hexafluorocobaltate(III)
Can you give the name of the following coordination compounds?
5. [CoBr(NH3)5]SO4
6. [Fe(NH3)6][Cr(CN)6]
7. [Co(SO4)(NH3)5]+
8. [Fe(OH)(H2O)5]2+
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
Answers:
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1. [Fe(NH3)6](NO3)3
2. (NH4)2[CuCl4]
3. Na3[FeCl1(CN)5]
4. K3[CoF6]
5. pentaamminebromocobalt(III) sulfate
6. hexaammineiron(III) hexacyanochromate (III)
7. pentaamminesulfatocobalt(III) ion
8. pentaaquahydroxoiron(III) ion
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
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SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL
เอกสารอ้างอิง
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•บทปฏิบตั กิ ารเคมีทวไป
ั ่ 1 มหาวิทยาลัยมหิดล
•จินตนา สิรพิ ทิ ยานานนท์, การวิเคราะห์โครงสร้างผลึก, พิมพ์ครัง้ ที่ 1, 2537.
•Emil J. Slowinski, Wayne C. Wolsey, William L. Masterton, Chemical
Principles in The Laboratory, 8th ed. Thomson Brooks/Cole Date
Published: 2000.
•Naming Coordination Compounds
http://www.chemistry.wustl.edu/~edudev/LabTutorials/naming_coord_comp.html
SORACHAI SAE-LIM, DEPARTMENT OF CHEMISTRY, MAHIDOLWITAYANUSORN SCHOOL