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CHEM 107
Inorganic Chemistry
Fall 2016
Review of General Nomenclature
Part 1
Ionic Compounds
Cations
(positively charged ions)
cations are always named first
most cations are monatomic
example: Na+ sodium ion (or sodium cation)
common polyatomic cation
CHEM 107
Inorganic Chemistry
Fall 2016
You are responsible for all of the monodentate ligands in the text book (refer to pp 317-318) and
the following chelating ligands.
1.
2.
3.
4.
5.
6.
7.
8.
9.
Ethylenediamine (en)
Diethylenetriamine (dien)
Tren
EDTA
A
ML6 Octahedral MO Diagram
2t1u
(n+1)p
x
y z
T1u
(n+1)s
s
A1g
nd
z2 x2y2 xy xz yz
Eg
T2g
2a1g
anti-bonding
ML *
2eg
t2g
M non-bonding
Energy
A1g
1t1u
1a1g
1eg
bonding
ML
Eg
T1u
ML6 Octahedral MO Diagram
It is also helpful to visualize the MOs so we unders
Recap: Chelate Ring Conformations
Chelating ligands also impart chirality because of the direction of
the chelate ring
M
M
isomer
isomer
Recap: Chelate Ring Conformations
Chelating ligands also impart chirality because of the direction of
the chelate ri
Ligand Substitution in SP Complexes
Ligand substitution in square planar transition metal complexes is of
critical importance in a variety of catalytic transformations
rates and substitution patterns (stereochemistry) follow regular and
predictable patter
Crystal Field Theory
(z2, x2y2)
eg
Energy
High Spin
10Dq = o
0.6o
or
Low Spin
0.4o
3d
3d
3d
Fe3+
Fe3+
Fe3+
(xy, xz, yz)
t2g
3d
Fe3+
Crystal Field Stabilization Energy (CFSE) is the energy difference for the
given electron distribution in the crystal fie
Crystal Field Theory: Tetrahedral Field
opposite splitting of
octahedral field
LL
z
Energy
M
x
L
y
L
L
barycenter
spherical field
t2 orbitals point more
directly at ligands and
are destabilized.
t2
e
e orbitals point less directly at
ligands and are stabi
Experimental Evidence for Electronic Structure
Electronic structure models seek to explain (and predict) the trends in
experimental data that are observed for coordination complexes
Thermodynamic data formation constants reflect relative ML bond strengths
"Selection Rules"
Transitions between orbitals with the same parity (symmetry with respect
to inversion) are Laporte FORBIDDEN!
d d both orbitals are symmetric with respect to inversion FORBIDDEN!
p p both orbitals are anti-symmetric with respect to inver
18 Electron Rule
The 18 electron rule is a loose formalism for describing stable electron
configurations for some transition metal coordination complexes.
18 electrons is the maximum number of valence electrons that can be accommodated by
the metal nd, (n
CHEM 107
Inorganic Chemistry
Fall 2016
Discussion Week of September 26th
Symmetry Operations:
E=
Cn =
Sn =
i=
h =
v =
Practice Problems - *Determine the point group of each of the following molecules*
1. Ethylene
6. PCl5
2. 1,1-dichloroethylene
7. IF7
3.
Guide to Symmetry, Orbitals, Bonding
Point Group Symmetry
Symmetry elements:
E = identity, nothing moves, (x, y, z) (x, y, z)
Cn = n-fold rotation axis, rotate by 2/n (highest value of n is the principle rotation axis)
Sn = improper rotation (rotat
CHEM 107
INORGANIC CHEMISTRY
FALL 2016
LECTURES. MWF 9:00 9:50 am in 1100 SSPA.
INSTRUCTOR. Professor A. S. Borovik
EMAIL ADDRESS. [email protected]
WEBSITE ADDRESS: https:/eee.uci.edu/16f/40720
LECTURE ASSISTANTS.
Victoria Oswald, [email protected]
Claudia
Midterm 2 Review Worksheet
1. An ammonium halide (NH4X) salt which crystallizes in the CsCl structure has a density of 2.431 g/cm3
and a volume of 66.87 . Determine the identity of the Ammonium Halide salt. Draw the unit cell for
CsCl.
2. Determine the oc
Crystal Structures
Chapter 7
Wednesday, October 21, 2015
Interstitial sites in CP Structures
A large number of ionic structures can be regarded as built of CP layers of anions
with the cations placed in interstitial sites
for every anion, there is 1 Octah
The Crystalline Solid State
Chapter 7
Monday, October 19, 2015
Midterm Exam I
this Friday, Oct 23, 9-9:50a
Chapters 4, 5, and todays part of 7 (no chapter 6)
multiple short answer problems testing basic concepts
closed book, closed notes
bring pen, pencil
MO Diagrams for
Linear and Bent Molecules
Chapter 5
Monday, October 12, 2015
Molecular Orbitals for Larger Molecules
1. Determine point group of molecule (if linear, use D2h and C2v instead of Dh or Cv)
2. Assign x, y, z coordinates
(z axis is principal a
MO Diagrams for
Diatomic Molecules
Chapter 5
Friday, October 9, 2015
Homonuclear Diatomic Molecules
What happens when we move to more complicated systems?
Consider O2.
The Lewis dot structure famously predicts the wrong electronic
structure for O2
We can
Symmetry and Point Groups
Chapter 4
Monday, September 28, 2015
Symmetry in Molecules: Staggered Ethane
So far we can say staggered ethane has three operations: E, C3, and C32
Symmetry in Molecules: Staggered Ethane
So we add three more operations: C2, C2,
Simple Molecular Orbital Theory
Chapter 5
Wednesday, October 7, 2015
Using Symmetry: Molecular Orbitals
One approach to understanding the electronic structure of molecules
is called Molecular Orbital Theory.
MO theory assumes that the valence electrons of
A Second Application of Symmetry
Chapter 4
Monday, October 5, 2015
Using Symmetry: Vibrational Spectroscopy
IR and Raman spectra can be interpreted using symmetry.
For nonlinear molecules, the number of vibrational modes
is 3N - 6, where N is the number o
Representations, Character Tables, and
One Application of Symmetry
Chapter 4
Friday, October 2, 2015
Matrices and Matrix Multiplication
A matrix is an array of numbers, Aij
column
matrix
columns
-1
3
1
-8
-1
7
2
2
rows
4
14
1
row matrix
3
1
2
3
4
To multi
Point Groups Continued
Chapter 4
Wednesday, September 30, 2015
Identifying Point Groups
The point group of an object or molecule can be determined by
following this decision tree:
See p. 81, Figure 4.7
Example: phosphorous pentafluoride
C3
C2
Does it belo
1. Determine the point group symmetry for the given molecules:
a) Cis-Cl2PtNH3
b) trans-Cl2PtNH3
c) trans-1,2-dichloroethylene
d) Deprotonated tetraphenylporphyrin
2. Using the molecule from part a, show the three ways to determine the order of the point
Mechanisms of Substitution Reactions
Interchange Mechanism
elementary (single-step) process with no observable intermediate
Associative Mechanism
multi-step process with one or more intermediates
incoming ligand coordinates to the metal complex before the
Reactions of Inorganic Complexes
Coordination compounds can adopt more complex geometries than
organic compounds, increasing reaction variability.
Selective, efficient, stable metal catalysts can improve the reaction
rates of many important transformati
CCM: Coordination Chemistry of
Transition Metals
Week 2 Spring 2016
Periodic Table of the Elements
Coordination Chemistry
Coordination compounds
compounds that include one or more metal atoms or ions and one or
more ligands that formally donate electrons