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1) Discuss syllabus
HCN
HCN
HCN
HCN
Can you draw a Lewis structure of HNC? Do you think it would be more or less
stable than HCN?
Draw the Lewis structure for CN (not CN). Draw a Lewis structure showing how
2
two CN molecules could react to form a more stable molecule.
SCN
FC: 1 0 0
FC: 1+ 0 2
SCN
SCN
Deciding between the final two structures depends on which atom can better
stabilize the extra negative charge
3
SCN
FC: 1 0 0
FC: 1+ 0 2
SCN
SCN
The answer depends on which atom can better stabilize the extra negative charge
H-O-H
(B)
NF3
(C)
NH3
H-N-H
FNF
All are
equivalent
(A)
(B)
(C)
(D)
Although bonds may be polar in a molecule, the dipole moments associated with
the polar bonds may cancel, leading to a non-polar molecule with polar bonds.
6
If all atoms are the same, which VSEPR structure type will have a dipole moment?
(A)
(B)
(C)
(D)
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
n = 3 = 2 m = 0 s=
n = 3 = 2 m = 0 s= -
n = 3 = 0 m = 0 s=
a or b
Radial wavefunction
Rn (r)
10
3s
3p
3d
Cannot be any of these
11
a) 4dxy
b) 4dx2-y2
c) 3dx2-y2
d) 5dxy
12
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
4) Interacting atomic
orbitals to form molecular
orbitals
Text: 2.2, 2.3, 5.1
13
a) 5s
b) 3dz2
c) 2s
d) 3s
outside view
sliced view
14
r22
r22
r22
r22
(all three)
r
A 4s, 3s, 2s
B 3s, 3p, 3d
C 4s, 4p, 4d
15
16
17
A (g) + e
18
Bond order =
Energy
?
He(2s )
1*
1sA
a) 1
b) 2
c) -1
d) 0
?
1sB
?
1
He(2sB)
Inorganic Chemistry I
Spring 2015
Prof. Jeffrey Rinehart
a) gerade
b) ungerade
c) neither
21
(pz + pz)
(pz pz)
Which of these combinations is antibonding?
a) pz + pz
c) both
b) pz pz
d)
neither
22
#2 (py py)
#1 (py + py)
y
#4 (px px)
#3 (px + px)
B) Only #1/#3
D) #1/#3 and #2/#4
23
pz px py
pz px py
atom a
atom b
pz pz
Which orbital interaction creates the most bonding and most antibonding combination?
a) px and px
b) py and py
c) pz and pz
d) px and py
24
pz px py
atom a
1u
1g
What should the unlabeled set of degenerate orbitals be labeled?
a) 2u*
b) 1u*
c) 1g*
d) 1u
pz px py
atom b
(py py)
(px px)
25
Example: O2
2*
1g*
2pz 2px 2py
2
1*
2s
2s
O
1
How many electrons does each EACH oxygen provide to this MO diagram?
a) 5
c) 6
b) 4
d) 8
26
Example: O2
2*
1g*
pz px py
pz px py
1u
2
1*
s
s
O
1
What is the highest occupied molecular orbital (HOMO) for O2?
a) 2
c) 1g*
b) 1u
d) 2*
27
Example: O2
2*
1g*
pz px py
pz px py
1u
2
1*
s
s
O
O
1
b) 1
d) 4
28
Inorganic Chemistry I
Spring 2015
Prof. Jeffrey Rinehart
2*
5
10
E
1*
2
2p
15
20
2p
1
2s
a) 1
b) 2
c) 3
d) 0
1*
25
30
35
2s
1
C
30
2*
a) carbon
b) oxygen
c) too complicated
d) equal
5
10
E
1*
2
2p
15
20
2p
1
2s
1*
25
30
35
2s
1
C
31
5
2p
10
E
15
2s
20
2p
25
30
35
40
45
boron
2s
fluorine
a) 2s
b) 2px
c) 2pz
d) no interaction
0
5
2p
1*
2s
2
1
10
E
15
20
1*
2p
25
30
35
40
45
boron
2s
fluorine
a) 1
b) 2
c) 1*
d) 1
0
5
2p
1*
2s
2
1
10
E
15
20
1*
2p
25
30
35
40
45
boron
2s
fluorine
Inorganic Chemistry I
Spring 2015
Prof. Jeffrey Rinehart
http://symmetry.otterbein.
edu/gallery/index.html
https://www.webmo.net/
Chapter 5 in book
4
5
* By definition, rotations
occur in a counterclockwise
fashion
3
C5
D4
C2
C6 and C3
C2
C2
C2
C2
38
C six
D eight
C six
D eight
A Yes
B No
41
A Yes
B - No
42
A Yes
B - No
43
A Yes
B - No
44
Inorganic Chemistry I
Spring 2015
Prof. Jeffrey Rinehart
http://symmetry.otterbein.
edu/gallery/index.html
https://www.webmo.net/
Chapter 5 in book
B6
C 10
D 14
Top
Side
Determining Molecular
Point Groups
n Cn
EXAMPLE:
A Td
B C3V
C D3h
D D3d
Determining Molecular
Point Groups
n Cn
EXAMPLE:
A Oh
B C2v
C Cv
D Dh
Determining Molecular
Point Groups
n Cn
H
EXAMPLE:
H
H
C
H
A Td
B D3d
C C3v
D Oh
Determining Molecular
Point Groups
n Cn
EXAMPLE:
A D2d
B C2h
C Cs
D C2v
Determining Molecular
Point Groups
n Cn
EXAMPLE:
A Td
B C3V
C D3h
D D3d
Determining Molecular
Point Groups
n Cn
EXAMPLE:
A Cs
B Ci
C D2d
D D2h
Determining Molecular
Point Groups
n Cn
EXAMPLE:
H3N
Cl
Pt
NH3
A Cs
B C4h
Cl
C D4h
D C2v
Determining Molecular
Point Groups
n Cn
EXAMPLE:
Co
A Cs
B C4v
C D4d
D D4h
Determining Molecular
Point Groups
n Cn
NH3
EXAMPLE:
H3 N
Mo
H3 N
CO
CO
CO
A D3h
B C3v
C Oh
D C2v
Determining Molecular
Point Groups
n Cn
CO
EXAMPLE:
H3N
Mo
H3N
NH3
CO
CO
A D3h
B C3v
C Oh
D C2v
FALSE
According to VSEPR theory, a molecule with steric number of four and two lone pairs FALSE
will be linear.
The orbital angular momentum quantum number (l) for a 3dz2 orbital will be the
same as for a 4dx2y2 orbital.
TRUE
In carbon monoxide (CO), the bonding MO made from 2p orbitals has more electron TRUE
density on the carbon atom.
FALSE
The radial probability function (~r22) describes the probability of finding an electron at
a given radius, summed over the surface area of the sphere described by that radius. TRUE
MO theory with s-p mixing predicts the paramagnetism (unpaired electron(s)) of B2. TRUE
58
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
So which Mulliken symbol describes the irreducible representation for this orbital?
In the C2v point group, an s-orbital centered at the origin (0,0,0) has a1 symmetry and will
therefore only interact with other orbitals that have a1 symmetry
So which Mulliken symbol describes the irreducible representation for this orbital?
In the C2v point group, an s-orbital centered at the origin (0,0,0) has b2 symmetry and will
therefore only interact with other orbitals that have b2 symmetry
?
x
So which Mulliken symbol describes the irreducible representation for this orbital?
Determining Molecular
Point Groups
a) D2h
c) Cv
b) C2h
d) Dh
63
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
y
2
1
x
65
G
# of irreducible
Representations
of a given type
1
=
h (order)
S
R
0
# operations
In class
Character of
Reducible
representation
Character of
Irreducible
representation
G = A1 + B2
z
y
x
a1
b2
b) py
c) pz
d) all
interact
67
z
N
H
69
2s
=?
What is the reducible representation of the 2s orbitals of the N2 SALC in C2h?
2s
a) 2 2 2 2
b) 2 0 2 0
c) 2 0 0 2
d) 2 0 0 2
70
=?
71
=?
72
=?
73
=2 0
0 2
Ag + B u
(2px/2px) = 2 0
0 2
Ag + B u
(2py/2py) = 2 0
0 2
Ag + B u
(2pz/2pz) = 2 0
0 2
Au + B g
(2s/2s)
By inspection, can you determine the irreducible representations of all of the NN SALCs?
a) 3Ag + 3Bu + 1Bg + 1Au b) 4Ag + 4Bu c) 2Ag + 2Bu + 2Bg + 2Au
d) None of these
74
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
We found three of the representations just by seeing how the Cartesian coordinates
transform in space. How do we find the last irreducible representation?
Properties of point groups:
1) The order of a group is equal to the total number of symmetry operations
What is the order of C2v?
a) 2
b) 6
c) 4
d) 3
75
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
b) 6
d) 3
76
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
b) 0
d) -1
77
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
7) All irreducible representations are orthogonal. (i.e. the sum of characters for two
classes multiplied together is zero)
Inorganic Chemistry I
Halloween Edition
Fall 2016
C2 Transformation Matrix
(x,y,z -x, -y, z)
?1 ?0
0 1
? ?
?0 ?0
0 x x
?
0 y = y
?
1
?
z z
?1
?0
?0
?0 x x
y = y
?0
?1
z z
s(xz)
z
y
x
?0
? 1
?0
s(yz)
z
1 0 0
0 1 0
y
x
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 1
0 1 1
80
C2 Transformation Matrix
(Rx, Ry, Rz Rx, Ry, Rz)
?1 ?0
0 1
? ?
? ?0
0
?1
0
?
?0
0 Rx Rx
?
0 Ry = Ry
?
1
?
Rz Rz
s(xz)
z
y
x
0 Rx Rx
?
0 Ry = Ry
?
?0 ?1
Rz Rz
?0
?1
s(yz)
z
1 0 0
y 0 1 0
x
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 1
0 1 1
81
2) Cn : ( = 1) A
( = 1) B
5) h :
3) i : ( = positive) g
( = negative) u
( = positive)
( = negative)
82
2) Cn : ( = 1) A
( = 1) B
5) h :
3) i : ( = positive) g
( = negative) u
( = positive)
( = negative)
83
2) Cn : ( = 1) A
( = 1) B
5) h :
3) i : ( = positive) g
( = negative) u
( = positive)
( = negative)
84
Inorganic Chemistry I
November 1, 2016
Prof. Alina Schimpf
0
0
1
B
cos 4 / 3 sin 4 / 3 0
sin 4 / 3 cos 4 / 3 0
0
0
1
sin 2 / 3 cos 2 / 3 0
cos 2 / 3 sin 2 / 3 0
0
0
1
1 0 0
0 1 0
0 0 1
86
A2
Rz
z2
87
Inorganic Chemistry I
November 3, 2016
Prof. Alina Schimpf
1
order
SR
# operations
In class
Character of
Reducible
representation
Character of
Irreducible
representation
x
C
A
y
C3v
2C3
3sv
1
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
Any vibrational mode that transforms in the same way as x, y, or z will have a net
shift in dipole moment and therefore be IR active
Which of these vibrational modes will show an absorption in the IR region?
2A1 and B1
A1 and B1
B1 and B2
92
Which orbital approaching along the z axis in the orientation shown is likely to
interact with the occupied orbital below to form a Lewis acid/base adduct?
occupied
occupied
occupied
y
x
occupied
unoccupied
LUMO (3d)
What is water in this case?
HOMO (4s)
Lewis acid
LUMO
Lewis base
HOMO
Oxidant
H2O
Ca
A&C
LUMO
What is water in this case?
HOMO
Lewis acid
Lewis base
LUMO
HOMO
Electrophile
F2
H2O
A&C
L
L
M
L
L
L
96
dx2-y2 dz2
dxz
L
dxy
dyz
L
M
What is the predicted crystal field splitting for a square pyramidal complex?
dxy
d z2
a)
b)
dz2 dx2-y2
dx2-y2 dxy
dxz dyz
c)
dx2-y2
d z2
dxy
dxz dyz
dxz dyz
d)
dx2-y2
dxy
d z2
dyz
dxz
97
dxz
dx2-y2
dyz
dx2-y2
dx2-y2 dz2
d z2
d z2
dxy
dxy
dxy
dxz
dyz
OCTAHEDRAL
dx2-y2 dz2
TETRAHEDRAL
dyz
dxz
SQUARE
PLANAR
d z2
dyz
dxz
SQUARE
PYRAMIDAL
dxy
dx2-y2
dyz
dxz
TRIGONAL
BIPYRAMIDAL
a) Tetrahedral
b) Square planar
c) Square Pyramidal
d) trigonal bipyramidal
98
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
[I] < [Br] < [Cl] < [N3] < [F] < [OH] < H2O
< NH3 py < [CH3] < [H] < [C6H5] < [CN] < CO
Pure donors
NH3
2a1
Metal
a) acid
b) base
100
[I] < [Br] < [Cl] < [N3] < [F] < [OH] < H2O
< NH3 py < [CH3] < [H] < [C6H5] < [CN] < CO
Weak field donors
Cl
Metal
a) acid
b) base
101
[I] < [Br] < [Cl] < [N3] < [F] < [OH] < H2O
< NH3 py < [CH3] < [H] < [C6H5] < [CN] < CO
Strong field acceptors
empty *
orbital
Metal
a) acid
b) base
red = 6 0 0 2 2 0 0 0 4 2
red = 6 0 0 2 2 0 0 0 2 2
red = 6 0 0 2 2 0 0 0 2 2
red = 6 0 0 4 4 0 0 0 2 2
103
order (h) = 48
red = 6 0 0 2 2 0 0 0 4 2
104
The a1g SALC has the same symmetry as an s-orbital. What must it look like?
The t1u SALCs have the same symmetry as the p-orbitals. What must they look like?
1 5 2 2 2 2
(dz2) =
4
2
red = 4 1 0 2 2
red = 4 0 2 2 2
red = 4 1 0 0 2
red = 4 1 0 0 4
108
order (h) = 24
red = 4 1 0 0 2
red = a1 + t1
red = a1 + t2
red = 2e
109
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
2) Use molecular
orbital theory to
explain the
spectrochemical
series
1 5 2 2 2 2
(dz2) =
4
2
a) None
b) All
c) Only dz2 dxz and dyz
d) Only dz2 and dx2y2
111
red = 4 1 0 2 2
red = 4 0 2 2 2
red = 4 1 0 0 2
red = 4 1 0 0 4
112
order (h) = 24
red = 4 1 0 0 2
red = a1 + t1
red = a1 + t2
red = 2e
113
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
115
[Co(H2O)6]2+
[CoCl6]4
[Co(CN)6]3
[Cu(CN)6]4
116
Energy
eg
t2g
Cu(II) Oh
xy
x2-y2
z2
xz
eg
eg
eg
Energy
eg
t2g
t2g
t2g
t2g
weak Jahn-Teller
(small distortion)
eg
eg
t2g
d electrons
High spin
Low spin
1
weak
2
weak
A
B
t2g
3
strong
?
weak
weak
strong
weak
strong
strong
C
strong
D none
weak
weak
weak
weak
strong
9
strong
I
N
C
R
E
A
S
I
N
G
d8 metal ions:
M(I)
M(II)
M(III)
rare
oxidation
states
[PdCl4]2-
[Ni(H2O)4]2+
[Ni(CN)4]2
[AuCl4]
3E
2E
2T
3T
2T
2
121
Racah parameter
(B in cm1)
Mn(II)
Fe(III)
Co(IV)
859
1029
1185
ionic
radius
(pm)
~75
~60
~53
Pd(II)
Pt(II)
Ni(II)
122
Racah parameter
(B in cm1)
Mn(II)
Fe(III)
Co(IV)
859
1029
1185
ionic
radius
(pm)
~75
~60
~53
any
d5 metal
Energy/B
A Mn(II), Fe(III) and Co(IV) complex all have the same ligand field.
Which line on the plot most likely corresponds to the Mn(II) complex?
2T
2
6A
o/B
123
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
(2S+1)L
d5
d3
ml = 2
-1
-2
What is the ground state term symbol for this electronic structure?
U(III): 5f3
ml = 3
-1
-2
-3
A
B
C
D
(4F)
L=0S
L=1P
L=2D
L=3F
L=4G
L=5H
L=6I
2A
4I
2F
4H
125
4A
E/B
2E
2E
2E
4T
1
4T None are
1 allowed!
A
6A
2T
1
C
1
Do/B
6A
2T
2
1
4A
E/B
2E
2E
2E
4T
1
4T None are
1 allowed!
A
6A
2T
1
C
1
Do/B
6A
2T
2
1
4A
2A
2
4T
1
4T
1
2A
4 A2
2E
4A2
4T
1
E/B
4T (4F)
1
4T
2
2T
2
2F
2T
1
2E
2G
4P
4A
4F
B) 2A1 4A2
Do/B
D) 2A2 4A2
128
Inorganic Chemistry I
Fall 2016
Prof. Jeffrey Rinehart
more antibonding
Energy
unoccupied orbitals
occupied orbitals
1s
Band
a)
b)
c)
d)
130
(A)
k
E
(C)
k
(B)
k
(D)
k
131