Documente Academic
Documente Profesional
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2014 2015
20142015
Part2:InorganicandOrganicChemistry
P
t2 I
i
dO
i Ch i t
G.Anantharaman
garaman@iitk.ac.in
Importantannouncements
Lectures: Feb.
Feb 24,
24 2015 - Apr.
Apr 17,
17 2015
Tutorial: Mar. 9, 2015 - Apr. 13, 2015 (every Monday)
Please note March 14, 2015 is a working day with Monday
class schedule. But there will be no tutorial for Section A
and B, instead a lecture for section A will be there between
9 00 - 9:50
9:00
9 50 h
hrs iin L7
L7.
Quiz (30 Marks): Mar. 27, 2015; 18:30 - 19:00 hrs (venue will
be announced later))
End Sem exam (120 Marks): 2 hrs (time and date will be
announced later by DOAA)
Iwillsendhomeassignmentsandyoucandiscusstheanswersinthe
tutorial
Section A
Section B
Lecture days,
Wednesday, Friday
Tuesday:16:00-16:50 hrs
times
Venue
L7
L7
Section A
Tutorial day
Monday
Ti
Time
9 00 - 9:50
9:00
9 50 hrs
h
Section
Venue
A1
L5
A2
L6
A3
L14
A4
L15
Tutors
Physical
Dr. Nisanth Nair,
M S
Mr.
Sarvesh
hK
K. P
Pandey
d
Dr. D.L.V.K. Prasad
Mr. Soumyadeb Dey
Dr. M. Chandra
Ms. Shalini Awasthi
Dr. K. Srihari
Mr. Chandan K. Das
Inorganic/Organic
Dr. S. K. Kundu
D M
Dr.
M. K
K. Gh
Ghoraii
Dr. A. K. Patra
Dr. D. H. Dethe
Dr. S. Basker
Dr. J. N. Moorthy
Dr. R. Angamuthu
Dr. A. Singh
Section B
Tutorial day
Monday
Time
Section
Venue
B1
L5
B2
L6
B3
L11
B4
L12
Tutors
Physical
Dr. S. R. Gadre
Mr. Gopal K. Dixit
Dr. T. G. Gopakumar
Ms Paramita Ghosh
Ms.
Dr. D. Goswami
Ms. Puspal Mukherjee
Dr. N. S. Gajpiye/
Dr. S. Manogaran
Mr. K. Sooraj
Inorganic/Organic
Dr. S. P. Rath
Dr. M. L. N. Rao
Dr. J. K. Bera
Dr R.
Dr.
R Gurunath
Dr. P. K. Bharadwaj
Dr. Y. D. Vankar
Mr. I. A. Bhat
Dr. R. Ramapanicker
Contents
Inorganic Chemistry
Crystal Field Theory: Structure and applications of Coordination
Complexes
Oxidative Addition
Addition, Reductive Elimination,
Elimination Insertion Reactions
Hydrogenation, Hydroformylation, Process and Ziegler-Natta
Polymerization
Organic Chemistry
Conformational Analysis of Alkanes and Cycloalkanes
Chirality
Substitution and Elimination Reactions
Books
Inorganic Chemistry by Shriver and Atkins
Inorganic
i Chemistry:
h i
Principles
i i l off Structure andd Reactivity
i i by
b
J E Huheey, E A Keiter and R L Keiter
O ga c Chemistry
Organic
C e st y by J C
Clayden,
ayde , N G
Greeves,
eeves, S Wa
Warren
e
Fundamentals of Organic Chemistry by T W G Solomons
5
Youwillcomeacross.
Natta
Ziegler
1955
~1890
~1920
2015
vanVleck
1927
Bethe
1930
SirGeoffreyWilkinson
1965
100yearsafterNobelprizethejourneycontinues.
N.P.E. Barry,P.J.SadlerPureandAppliedChemistry,2014,Volume86,Pages18971910
Cyclicpolyethersandtheircomplexeswithmetalsaltsandcircularhelicate
O
O
18crown6potassium
O
O
O
ThesimplereactionofatrisbpyligandstrandwithFeCl2 leadsto
theselfassemblyoftheuniquecation1,whichconsistsofa
II ionsina
torusformedbyfiveligandswrappedaroundfiveFe
y
g
pp
doublehelicalfashionandclosedaroundacentralchlorideion.
Thisstructure,afivefoldcircularhelicate,isahelicateanalogue
ofcircularDNA.
C.J.Pedersen,J.Am.Chem.Soc.,1967,89(26),pp70177036
8
AngewandteChemieInternationalEditioninEnglish,year1996, Volume35,pages18381840.
Molecularmachinesandnanotechnology
In this example of a molecular machine we are able to switch between two molecular states (shapes) in a
controlled manner as part of a repetitious mechanical cycle. An azobenzene molecule can exist in two forms
((left: trans with the bulkyy ggroups
p on opposite
pp
sides of the double bond, and right:
g cis with the bulkyy ggroups
p on
the same side). The bulky groups can be moved closer together or further apart by switching between the cis
and trans forms. This switching can be performed by using light of two different colours, one to go from cis to
trans, the other to reverse the process.
W.R.BrowneandB.L.FeringaNatureNanotechnology2006,1,25 35.
M.F.Hawthrone,Science,2004,303,18491851
Lightdrivenunidirectionalrotarymotorsinaction
a, Principle of cistrans isomerization around a double bond connecting two groups (R). Light absorption induces a rotary
motion around the double bond,
bond which results in a change in the relative position of the two R groups.
groups b,
b Examples of
first and secondgeneration rotary motors that operate by photochemical cistrans isomerization (Meax and Meeq
indicate axial and equatorial orientations of the methyl groups, respectively). c, Secondgeneration rotary motor
immobilized on a gold surface. The first photochemical transtocis isomerization forces the molecule into a highly
strained cisgeometry. Rotary motion continues in the same direction as the consequence of a thermal helix inversion that
results in a release of the strain in the molecule. Subsequent irradiation induces a cistotrans isomerization, which is
followed by a second thermal helix inversion, again with release of conformational strain, to provide the initial state.
10
W.R.BrowneandB.L.FeringaNatureNanotechnology2006,1,25 35.
Transienthemiaminaltrappedinaporousnetwork
11
Zn4O
Yaghi et al. Science 2003, 295, 469.
12
HybridMetalOrganicFrameworks(MOFs):UpcomingMaterialsforGas
Adsorption/Storage/Sieving
MOFsareframeworkstructuresconsistsofmadeofMetalsandorganic
ligands asnodesandlinkers
TheyhaveapotentialapplicationsinGas/liquidsorption,luminescence,
They have a potential applications in Gas/liquid sorption luminescence
magnetismandcatalysis
Recentlythefocusisgiventodevelopfunctionalcoordinationpolymers
VeryrecentlytheBASFfurthertestedthe
l h
f h
d h
nanocubes ofMOFsasmaterialstoincreasefuel
fuelstoragecapacityinNaturalGasVehicles
The major efforts are going on to develop porous materials with high capability
of storing gaseous molecules such as H2, O2, CO2, and other obnoxious gas
emission from vehicles and transform to usable materials
The key is the modulation of the final structure using appropriate choices of
connectivity in metal and organic ligands
BASF: https://www.youtube.com/watch?v=nSP-VDwKz5o&list=PLvd4K_EStw4iqKi6xo6RkGV9-cbULkceg&index=19
13
BASF: BadischeAnilin undSodaFabrik
carotene
PolyvinylChloride(PVC)
Polystyrene
14
Gum base
Whatt is
Wh
i gum made
d off today?
t d ?
Gum base gives gum that bounceback texture that makes it fun to chew. Each company
keeps their special recipe for gum base a secret, but there is something we can tell
yyou... All ggum bases are made of three kinds of ingredients
g
which ggive ggum its special
p
properties:
Resin the main part you chew
Wax softens the gum
Elastomer adds flexibility
Gumbaseoftencontainspolyethylene(pah
leeethleen),alongmoleculethat'salsoused
tomakeplasticbottlesandplasticbags.
KarlZiegler
GiulioNatta
TheNobelPrizeinChemistry1963
15
http://www.acs.org/content/acs/en/education/whatischemistry/adventuresinchemistry/secretsciencestuff/gum.html
Metallodrugs
Amongthenaturalsciences,medicinalinorganicchemistryisstillconsidereda
rather young discipline by many, but this is contrary to the historically proven
ratheryoungdisciplinebymany,butthisiscontrarytothehistoricallyproven
useofmetalsinpharmaceuticalpotions,whichtracesbacktotheancient
civilizationsofMesopotamia,Egypt,India,andChina
Ehrlich ssalvarsaniswidelyregardedasthe
Ehrlichs
salvarsan is widely regarded as the
birthofmodernchemotherapy
O
O
H3N
Pt
H3N
O
O
contrastagentscontaining
contrast
agents containing
radioactivemetalisotopes
16
FromChemicalengineer@IITKtotumorpathophysiology
NH
N
N
N
N
HO
Cl
Losartan
RakeshK.JainistheAndrewWerkCookProfessorof
Rakesh
K. Jain is the Andrew Werk Cook Professor of
TumorBiologyatMassachusettsGeneralHospitalin
theHarvardMedicalSchool.Dr.Jainprimarily
researchestumorpathophysiology
17
18
Periodic table
Noneedtomemorizeyouwillbeprovidedintheexam
19
Compound
CoCl3 6NH3
CoCl3 5NH3 H2O
CoCl3 4NH3
CoCl3 4NH3
Color
No.andequivofAgCl ppt.
orangeyellow
3
red
2
purple
1
green
1
20
ProposedStructuresfor6CoordinateCobalt(III)complex
21
Ligands
Neutral molecules or ions having a lone electron pair that can be used to form a bond to
a metal ion.
M
Monodentate
d
ligand
li
d one bond
b d to a metall ion
i
N
O
H
H
water
Cl-
chloride
H
ammonia
carbon monoxide
C
N
cyanide
S
C
N
thiocyanate
22
23
Isomerism
On finding compounds with different properties follow the chart below
24
Linkage Isomerism
Occurs with ambidentate ligands. These ligands are capable of coordinating in more
than one way. The best known cases involve the monodentate ligands SCN / NCS and
NO2 / ONO.
25
Ionization Isomerism
Theyy form different ions in solution.
[Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4
[PtBr(NH3)3]NO2 and [Pt(NO2)(NH3)3]Br
Coordination Isomerism
Found in compounds in which both cations and anions are complexes, through the
exchange of some ligands from the cationic part to the anionic part
[Co(NH3)6] [Cr(C2O4)3] and [Co(C2O4)3] [Cr(NH3)6]
[Zn (NH3)4] [CuCl4] and [ZnCl4] [Cu(NH3)4]
Hydrate Isomerism
Through the replacement of coordinated groups by water molecules
[CrCl2(H2O)4]Cl2H2O (bright-green)
[[CrCl(H
( 2O))5]]Cl2H2O (g
(grey-green)
yg
)
[Cr(H2O)6]Cl3 (violet)
26
Geometrical Isomerism
Geometrical isomerism is ppossible with square
q
pplanar and octahedral complexes
p
but not
with tetrahedral complexes.
Square
q
planar Complexes
p
p
Ma2b2 2 isomers are possible (cis and trans)
NH3
Cl
Pt
Cl
Cl
NH3
trans
Cl
Pt
NH3
NH3
cis
27
Geometrical Isomerism
Octahedral Complexes
Ma4b2 2 isomers are possible (cis and trans)
NH3
Cl
H3N
H3N
H3N
H3N
NH3
NH3
Co
Co
NH3
Cl
Cl
cis
Cl
trans
M 3b3 2 isomers
Ma
i
are possible
ibl (fac
(f andd mer))
NH2
Cl
en
Cl
Co
en
Co
en
en
is
Cl
en
cis
Cl
trans
NH2
28
Optical Isomerism
Optical isomers are related as non-superimposable mirror images and differ in the
direction with which they rotate plane-polarized light. These are possible for both
tetrahedral and octahedral complexes, but not square planar.
Left handed
Right handed
29
Co(III) d6 e-
TheNobelPrizeinPhysics1967wasawardedtoHansBethe"forhis
contributions to the theory of nuclear reactions especially his
contributionstothetheoryofnuclearreactions,especiallyhis
discoveriesconcerningtheenergyproductioninstars".
Krishnan,K.S.andMookherji,A.,Phys.Rev.51,428and774(1937)
32
d orbitals
(dx2
y ,
o
M+L
(dxy, dyz, dxz)
spherical
(free-metal
(free
metal ion)
M L6
dz2 )
Octahedral Field
To sum it up...
p
Metal ions are attracted to the electron pairs in ligands
The lone pair of electrons in the ligands repel the electrons present in
the d orbitals
These interactions are called crystal field
Such interactions affect the energy of the d orbitals but not uniformly
E nergy
dx2-y2, dz2
d orbitals in a
spherical field
Energy
eg
3/5 or 0.6o
o
Barry centre
2/5 or 0.4 o
t2g
The higher energy set of orbitals (dz2 and dx2-y2) are labeled as eg, a doubly degenerate
(e) orbital with gerade (g) symmetry, and the lower energy set is labeled as t2g , a triply
d
degenerate
t (t) orbital
bit l with
ith gerade
d (g)
( ) symmetry.
t These
Th
notations
t ti
are based
b d on the
th
symmetry of the orbitals.
The energy separation between the two levels is denoted by o or 10 Dq.
To maintain the average energy, the eg orbitals need to be repelled by an amount of 0.6
o and the t2g orbitals to be stabilized to the extent of 0.4 o.
eg
Enerrgy
3/5 or 0.6o
3/5 or 0.6o
o
Barry centre
Barry centre
2/5 or 0.4 o
t 2g
2/5 or 0.4 o
t 2gg
Examples: [V(H2O)6]3+
Examples: [Ti(H2O)6]3+
d5
1 u.e.
5 u.e.
d6
0 u.e.
4 u.e.
d7
1 u.e.
3 u.e.
OCTAHEDRON
TETRAHEDRON
Ligands approach through alternate corners
Absence of centre of symmetry
Tetrahedral Field
Energy
t2
2/5 t
t
3/5 t
Energyy
Octahedral Vs Tetrahedral