CY1001
Exam pattern:
• Quiz I (4th Sep, 8 am)
• Quiz II (16th Oct, 8 am)
• End-sem (19rd Nov)
Attendance:
• Highly Important
• Institute Norm
Syllabus:
• Transition metal chemistry
• Organometallic Chemistry
• Aromaticity
• Aromatic Substitution Reactions
• Pericyclic reactions
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CY1001
Inorganic Part
• Transition metal chemistry (5 classes)
Bonding in transition metal complexes; coordination compounds; crystal field theory,
octahedral, tetrahedral and square planar complexes; CFSE; Jahn-Teller theorem;
Spectral, electronic and magnetic properties of coordination complexes.
• Organometallic chemistry (5 classes)
Synthesis structure and reactivity of metal carbonyls; 16 and 18 electron rules;
Variety of ligands and hapticity; Type of reactions: Oxidative addition,
Reductive elimination, Migratory insertion; Homogeneous catalysis, Hydrogenation,
Hydroformylation, Monsanto process, Wacker process.
Text Books:
1) Inorganic Chemistry: Principles of Structure and Reactivity
by Huheey, Keiter and Keiter, 4th Edition
2) Inorganic Chemistry by Shriver and Atkins 4
CY1001
Organic Part
• Aromaticity (4 classes)
Aromatic, non-aromatic and anti-aromatic compounds. Aromatic nucleophilic
substitution reactions.
• Pericyclic reactions (6 classes)
Definition, classifications, electrocyclic reaction of butadiene and hexatriene,
photochemical [2+2] and thermal [4+2] cycloadditions, Sigmatropic rearrangements -
limited to Cope and Claisen rearrangements, FMO approach - Woodward Hoffmann
rules and basic stereochemistry aspects of the above reactions.
Textbooks:
1) Organic Chemistry by P. Bruice, Prentice Hall, New Delhi, 3rd Edition, 2001
2) Organic Chemistry by Clayden, Warren, Greeves
3) Organic Chemistry by J. McMurray
4) Advanced Organic Chemistry, PART A, by Francis A. Carey and Richard J.
Sundberg
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Importance of Transition metal complexes
Dyes and Pigments Analytical Chemistry
Phthalocyanine Blue Gravimetric Analysis Ni(DMG)2 Sequestering Agents
Extraction of metals
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Importance of Transition metal complexes
Biological Molecules Chemotherapy Gems
Ruby – Sapphire–
Hemoglobin Corundum Corundum
cis-platin
(α-Al2O3) + (α-Al2O3) +
trace ‘Cr’ trace ‘Ti/Fe
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Transition Metals
Definition: Element which has a partially filled ‘d’ shell or which can
give rise to cations with an incomplete ‘d’ shell or in the ‘d’ block of the
periodic table (group 3-12)
The ‘f’ block (Lanthanide and actinide) elements are also considered
transition metals and are called “inner transition metals” 9
Transition Metal Chemistry
• Filling of 3d, 4d, 5d shells
• Most of the elements have incompletely filled d-shell (interesting
properties)
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Transition Metals - Properties
• Almost all: HARD, STRONG; High m.p., b.p.
• Conduct heat & electricity
• Form Alloys
• Show variable oxidation states
• At least one of the ions & compounds colored
• Form paramagnetic species because of partially filled shells
• Catalytic property
• Form coordination compounds (complexes) and organometallic
compounds
This course will introduce you to some aspects of 3d (Sc-Cu) transition metals
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Electronic configurations
For elemental state
The 3d orbitals fill after the 4s:
1s < 2s < 2p < 3s < 3p < 4s ≤ 3d < 4p < 5s ≤ 4d < 5p < 6s ≤ 4f ≤ 5d < 6p
22Ti = 1s2 2s22p6 3s23p6 4s23d2
The configuration of the first row transition metals (elemental state)
(apart from Cr and Cu) is [Ar]4s23dn-2 rather than [Ar]3dn.
The electronic configuration for the ions are different from the element:
they are all dn, the 4s are not filled. Ti3+ = 1s2 2s22p6 3s23p63d1 4s0
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1st Row Transition Metals – Electronic configuration/Oxidation state
Electronic configuration Oxidation state
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Coordination complexes
Compounds which consist of d-block transition metal-ions (Mn+) and
ligands (L) (neutral or anionic nonmetal species) are referred to as
coordination complexes
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Coordination complexes
• Coordination Number (CN): The number of ligands around the
metal.
• Denticity: The coordination mode of the ligand. MONO-
dentate, Bi-dentate or POLY-dentate (dentātus = teeth in Latin)
• Oxidation State: The formal charge on the metal (normally
postive), taking into account the charges on ligands and the
overall charge of the complex. This, in turn leads to the number
of d-electrons on a metal.
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Coordination complexes
Coordination Number:
The number of ligands around the metal.
Here, 6
Oxidation State:
The formal charge on the metal
Here, 3+
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Different metal ions
Central metal ions
• Property differences between the 3d and the 4d series are much more than
between the 4d and 5d metals
• Metal complexes of the 3d transition metals are rarely seven co-ordinate
• M(II) and M(III) oxidation states are common among the first (3d) series
• Higher oxidation states than M(II/III) are considerably more stable in the
second and third series transition metals
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3 4 3,4,5 3,6 2,7 2,3 2,3 2 1,2 2
Some stable common oxidation states of transition metal ions (3d series)
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Different types of ligands
• Ligands are inorganic or organic molecules (neutral or anionic) bonded to
the central metal ion
• Those ligands with a single ligating atom are called monodentate ligands,
and those with more than one ligating atoms referred to as polydentate
ligands (chelate ligands).
Common monodentate ligands
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Different types of ligands
Common bidentate ligands
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Different types of ligands
Common multidentate (chelate) ligands
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