Gaussian Calculations of

Simple Organometallic
Molecules: technical aspects
Practical theoretical chemistry

Camerino (Italy), 7 - 18 August 2012

Presentation
Prof. Agustn Galindo ([email protected] )
http://personal.us.es/galindo/
Research Group:
Organometallics and Homogeneous Catalysis
http://grupo.us.es/gfqm223/
Inorganic Chemistry Department
http://departamento.us.es/dinorganica/
University of Sevilla
http://www.us.es

Gaussian Calculations of Simple Organometallic Molecules:

technical aspects
- Introduction
- Practical theoretical chemistry

- Types of complexes to be analyzed

- Gaussian program

- Metal carbonyls

- Input file

- Metal olefin complexes

- Running the calculation

- Information from output

- Theoretical chemistry on paper

Introduction
Selected Bibliography:
- Molecular Orbitals of Transition Metal Complexes, Y. Jean, Oxford
Univ. Press, 2005.
- Orbital Interactions in Chemistry, T.A. Albright, J.K. Burdett, M.H.
Whangbo, Wiley, 1985.
- An Introduction to Molecular Orbitals, Y. Jean, F. Volatron, J. Burdett,
Oxford Univ. Press, 1993.
- Problems in Molecular Orbital Theory, T.A. Albright, J.K. Burdett,
Oxford Univ. Press, 1992.
- Computational Chemistry, D. Young, Wiley, 2001.
- Introduction to Computational Chemistry, F. Jensen, Wiley, 1999.
- Exploring Chemistry with Electronic Structure Methods, J. B.
Foresman, . Frish, Gaussian, 1996.
- Density-Functional Theory of Atoms and Molecules, R. G. Parr, W.
Yang, Oxford University Press, 1989.

Some useful links:

Introduction

Glossary of Common Terms and Abbreviations in Quantum Chemistry

http://cccbdb.nist.gov/glossary.asp
The Absolute Beginners Guide to Gaussian (David Young)
http://www.ccl.net/cca/documents/dyoung/topics-orig/gaussian.html
Background Reading for Basis Sets
http://www.shodor.org/chemviz/basis/teachers/background.html
UNIX Tutorial for Beginners
http://www.ee.surrey.ac.uk/Teaching/Unix/
vi Editor Commands
http://www.cs.rit.edu/~cslab/vi.html
Etc.

Introduction
BACK
Every attempt to employ mathematical methods in the study of
chemical questions must be considered profoundly irrational and
contrary to the spirit of chemistry.
Auguste Compte, French philosopher, 1830
TODAY
Computational chemistry is a standard tool of science. For example,
there are now >20 journals devoted to the subject.
Chemometrics and Intelligent Laboratory Systems
Computational and Theoretical Polymer Science
Electronic Journal of Theoretical Chemistry
International Journal of Quantum Chemistry
Journal of Chemical Information and Computer Sciences
Journal of Chemical Theory and Computation
Journal of Chemometrics
Journal of Computational Chemistry
Journal of Computer Aided Chemistry
Journal of Mathematical Chemistry
Theoretical Chemistry Accounts (Theoretical Chimica Acta)

Journal of Molecular Graphics and Modelling

Journal of Molecular Modeling
Journal of Molecular Structure: THEOCHEM
Journal of the Chemical Computing Group
Journal of Theoretical and Computational Chemistry
Macromolecular Theory and Simulations
Perspectives in Drug Discovery and Design
Proteins Structure, Function, and Genetics
Structural Chemistry

Introduction
Computational Chemistry, D. Young, Wiley, 2001.
At

one

time,

computational

chemistry

techniques were used only by experts extremely

experienced in using tools that were for the most
part difficult to understand and apply. Today,
advances in software have produced programs
that are easily used by any chemist

TODAY
I am

any chemist

You are

any chemists

Introduction

What type of calculations?

DFT (Density Functional Theory)
DFT is a exact re-formulation of quantum mechanics in terms of
probability density instead wave function.
The ground state energy was obtained from a minimization of the E[ ]
functional (this functional exists, but is unknown). The Kohn-Sham
method is the employed methodology.

The Nobel Prize in Chemistry 1998

"for his development of the
density-functional theory"

Introduction
http://nobelprize.org/
"for his development of
computational methods in
quantum chemistry"

Walter Kohn

John A. Pople

1/2 of the prize

1/2 of the prize

USA

United Kingdom

University of California
Santa Barbara, CA, USA

Northwestern University
Evanston, IL, USA

b. 1923
(in Vienna, Austria)

b. 1925
d. 2004

Introduction
References from SciFinder database for Quantum Chemistry and
Density Functional Theory (last 10 years).

Number
of hits

2001

2002 2003
2004

2005 2006

2007

2008

2009 2010

2011

Introduction

Publications on Web of Science for the years 19942008

with the topics density functional theory (DFT) and B3LYP.

Dalton Trans., 2010, 39, 296.

Introduction
Percentage share of papers with the topic density functional theory
or DFT in the more general areas of organometallic and
homogeneous catalysis (19962008, Web of Science).

Dalton Trans., 2010, 39, 296.

Introduction

RMS Deviation ()

Deviation between calculated and experimental bond lengths for

several families of compounds as a function of the calculation type.
0.20

HF
MP2

0.15

SVWN
BLYP
B3P86

0.10

B3LYP

0.05

Oxides

Fluorides

Carbonyls

Hydrides Organometallics Chlorides

Introduction

What type of program?

Gaussian
http://www.gaussian.com/
An electronic structure package capable of predicting many
properties of atoms, molecules, reactive systems, (e.g.; molecular
energies, structures, vibrational frequencies, electron densities, )
utilizing ab initio, density functional theory, semi-empirical,
molecular mechanics, and various hybrid methods.

Introduction

Gaussview
http://www.gaussian.com/gv_plat.htm
Graphical interface for Gaussian
build molecules or reactive systems
setup Gaussian input files
graphically examine results
Additional information about
Overview of Capabilities and Features
See: http://www.gaussian.com/g_prod/gv5b.htm

Introduction

Where?

Centro Informtico Cientfico de Andaluca

Introduction

Where?

Camerino

SSH

CICA

PC room

protocol

pool.cica.es

Gaussian Calculations of Simple Organometallic Molecules:

technical aspects
- Introduction
- Practical theoretical chemistry

- Types of complexes to be analyzed

- Gaussian program

- Metal carbonyls

- Input file

- Metal olefin complexes

- Running the calculation

- Information from output

- Theoretical chemistry on paper

Login:
- From your terminal, open the SSH program

Login:
- In the SSH window open Quick Connect

Login:
- In the SSH window open Quick Connect

Login:
- Write:

Host name:
User Name

pool.cica.es
eucheme#

(where # is 01-25)

Click
eucheme01

Login:
- Write your password:

acaoc#0809

(where # is 01-25)

Login:
- You are at CICA (Sevilla) in your account:
eucheme#@pool.cica.es
(where # is 01-25)

Policy:
- Each student must work exclusively on the assigned account.
- The system works with queues (it is forbidden to run interactively
any program) and it is necessary to create the specific script file
lanza.sge (example in your account) to run the Gaussian program.
- For working on the CICA system (pool.cica.es), it is necessary to
known a few UNIX commands and also to know the use of vi editor.
Selected UNIX and vi commands are available at:
http://personal.us.es/galindo/Commands.pdf

- Practice for a few minutes with the UNIX commands

List files in directory

ls

You have the files: NiCO4.com and lanza.sge *

To know the working directory

pwd

This is: /home/eucheme#

Copy file f1 into f2

cp f1 f2

Delete (remove) file f2

rm f2

List file contents by screen

more f1

* NiCO4.com
lanza.sge

is the input file of the Ni(CO)4 molecule.

is the script file for submitting the job.

- Edit the file NiCO4.com and practice a few minutes with vi commands:
> vi NiCO4.com
move to the last line in the file
delete character under cursor
delete line under cursor
replace character under cursor with
next character typed
finds a word going backwards
finds a word going forwards
undoes last command issued

G
x
dd
r
?word
/word
u

IMPORTANT:
Do not use the mouse with the vi mode.
Do not change now the files, exit with :q!
To exit vi and save changes
To exit vi without saving changes

:wq
:q!

- Edit the file lanza.sge and practice a few minutes with vi commands:
> vi lanza.sge
Inserting
insert before cursor

append after cursor

open line above cursor and

enter append mode

To enter vi command mode

[esc]

IMPORTANT:
Do not use the mouse with the vi mode.
Do not change now the files, exit with :q!

- To submit a job and run the Gaussian program it is necessary to

prepare the corresponding script file: lanza.sge (it exists in your
directory)
- When you have edited this file, its structure is:
#$
#$
#$
#$
#$
#$

-S /bin/bash
-N pruebaGaussian
-cwd
-q acaoc
-o IP.out
-pe make 2

export
export
export
export

g03root=/home/deposito/G03Linda/
G03BASIS=/home/deposito/G03Linda/g03/basis
GAUSS_ARCHDIR=/home/deposito/G03Linda/g03/arch
GAUSS_EXEDIR=/home/deposito/G03Linda/g03/bsd:/home/deposito/G03Linda/g03

/home/deposito/G03Linda/g03/g03 /home/eucheme01/NiCO4.com

Order to execute the program

Input file to be calculated

Gaussian program

Gaussian files:

Input

Gaussian

Output

Read carefully the document GaussFiles.

See it at
http://personal.us.es/galindo/GaussFiles.pdf
More information at
http://www.gaussian.com/

- To run the Gaussian program it is necessary to prepare the

corresponding input file: NiCO4.com (it exists in your directory)
- When you have edited this file, its structure is:
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Gaussian program
Input file structure
Filename.com
(or Filename.inp or Filename.gjf)
Free format, case insensitive
Spaces, commas, tabs as delimiters between keywords
! as comment line/section
Divided into sections (in order)
Link 0 commands (%)
Route section what calculation is to do
Title
Molecular specification
Optional additional sections

Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

Link 0 commands
Route section
Title
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Molecular
Specification

Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt

Link 0 commands

Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Gaussian program
Link 0 commands
Locate and name scratch files; System Resources Required
Not blank line terminated
Some Link 0 options (Examples)
%chk
%chk=name.chk
(Location and name of checkpoint file)
%mem
%mem=1Gb
(Sets the amount of dynamic memory, default is 32Mb.
Units allowed: kb, mb, gb, kw, mw, or gw.)
%nproc
%nproc=2
(Sets the number of processors to use)

Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt

Route section

Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Gaussian program

Route section

Specify desired calculation type, model chemistry and other options

Start with # , can be multiple lines
Blank line terminated
Keywords can be specified in any order
Options are grouped in parentheses, ()
Keywords should not be repeated
Route section can be up to 5 lines long
3 key components to this specification:
The method
The basis set
The job type
Syntax: Method

Basis Set

Job type

Route section

Gaussian program

Selected job types

SP
(Single point energy. Default)
Opt
(Geometry optimization.)
Freq
(Frequency and thermochemical analysis)
Selected methods
HF
(Hartree-Fock calculation, by default, RHF for singlets
and UHF for higher multiplicities)
B3LYP
(DFT calculation with B3LYP functional)
MPx
(HF calculation and a MPx correction (x=2, 3, 4, 5))
CCD
(CCD calculation)
CCSD
(CCSD calculation)
CID
(CI doubles only calculation)
CISD
(CI singles and doubles calculation)
AM1
(semiempirical calculations with AM1)
PM3
(semiempirical calculations with PM3) no basis set spec
needed

Route section
Some basis sets:

Gaussian program

STO-3G, 3-21G, 6-21G, 4-31G, 6-31G, 6-311G

Polarization: *, **
6-31G*=6-31G(d), 6-31G** = 6-31G(d, p)
Diffuse functions: +, ++

Background Reading for Basis Sets

http://www.shodor.org/chemviz/basis/teachers/background.html

Route section

Gaussian program

Selecting a Basis Set : Quick Reference

Note: At least 6-31G needed for research

Standard for our calculations: 6-31G*

Gaussian program
Route section
#N
#P

(normal print level (default))

(additional output is generated)

TEST

(do not save an archive file)

Geom

(specify source of molecular specification input)

=connection
(specify explicit atom bonding data via
additional input section)
=check
(take input from checkpoint file)
=allcheck
(everything from checkpoint file)

Guess

(initial guess of HF wavefunction)

=check
(read from checkpoint file)
=only
(terminate calc. once guess is done)

Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

Title section
Brief description of
calculation (cannot
exceed five lines)
Title
0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

Blank line terminated

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Gaussian program
%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt
Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Molecular
Specification

Gaussian program
Molecular Geometry
1st line: Charge and spin multiplicity (2S+1)
Element label and location
Cartesian coordinates
Label x y z
Z-matrix
Label atoms bondlength atom2 angle atom3 dihedral
Blank line terminated

Gaussian program
System Resources

%mem=1GB
%nproc=2
%CHK=NiCO4.chk
# B3LYP 6-31G* opt

Checkpoint File
Computational Model
Calculation Type

Ni(CO)4 Td
0 1
Ni
C
O
C
O
C
O
C
O

Title
Charge & Multiplicity

0.000000
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458
1.045712
1.707458

0.000000
1.045712
1.707458
-1.045712
-1.707458
1.045712
1.707458
-1.045712
-1.707458

0.000000
1.045712
1.707458
1.045712
1.707458
-1.045712
-1.707458
-1.045712
-1.707458

Structure
Cartesian
Coordinates

EXERCISE 1:

Ni(CO)4

Optimize the following compound:

Name of the input file: NiCO4.com

See structure at:

http://www.3dchem.com/3dmolecule.asp?ID=96

Ni(CO)4 contains nickel in the zero oxidation state (d10). It has 18

valence electron, and is a tetrahedral molecule with four carbonyl ligands
attached to nickel. Ni(CO)4 was first synthesised, as a pale-yellow liquid,
in 1890 by Ludwig Mond by the direct reaction of nickel metal with CO. It
is an intermediate in the Mond process for the purification of nickel and a
reagent in organometallic chemistry. It is a extremely toxic compound.

Running the calculation

Gaussian

Input

Output

- To submit a job and run the Gaussian program, type:

> qsub lanza.sge
(an ID number is created for your job)
- To see the jobs in queue or running, type:
> qstat
The system replies, for instance:
job-ID

name

user

state

submit/start at

queue

--------------------------------------------------------------------------------------351443

pruebaGaus eucheme08

07/06/2012 18:05:51

running

[email protected]

- When the program is running there are several files (type Gau-*.*)
that disappear when the work is correctly finished. Type:
> ls
to see these files.

- You can check the evolution of your calculation by the command

qstat and also by editing the file NiCO4.log (with the vi program) .

- The presence of a file named core.* indicates an error.

- When the calculation is finished, it is necessary to check the *.log file.

Edit the NiCO4.log file (with the vi program) and:

- go to the end of the output file (press G) and see:
Normal termination of Gaussian 03 at

- type ?YES

and see four YES and:

Optimization completed.
-- Stationary point found.

Information from the output files: NiCO4.log

- Optimized structure and the corresponding structural

parameters (bond distances and angles, ).
- Spectroscopic data (IR, Raman, NMR, ).
- Molecular orbitals.

Use of Gaussview program

From the SSH program, open the SSH File Transfer Client

Your terminal at Camerino ||

CICA (Sevilla)

Transfer the NiCO4.log file from CICA to your terminal

From your terminal, open the program

Go to Open file

Select *.log as File type

and open the file: NiCO4.log

EXERCISE 2:
Run frequency calculations on the optimize Ni(CO)4
compound.

The optimization carried out with Ni(CO)4 molecule afforded

the geometry of a stationary point. It is necessary to check if this
point is an actual global ground state (NImag = 0) or a transition
state (NImag = 1) through the calculation of frequencies. This
calculation computes force constants and the resulting
vibrational frequencies.

Gaussian program
Checkpoint file
For example: NiCO4.chk

When a subsequent calculation is to use results from a

previous calculation as its inputs, these results can be kept in
a special file to avoid having to type them into the new input
file. Many such results are put in a file called a checkpoint file.
It is a binary file. The use of a checkpoint file can be specified
using the correct options on line 0 commands at the input
file.

Gaussian program
Use of Checkpoint file. Example: Frequency calculations:
- At CICA: copy the files NiCO4.com and NiCO4.chk to NiCO4f.com and
NiCO4f.chk :
> cp NiCO4.com NiCO4f.com

> cp NiCO4.chk NiCO4f.chk

- Edit the NiCO4f.com and change it until:

%mem=1GB
%nproc=2
%CHK=NiCO4f.chk
# B3LYP 6-31G* geom=check guess=check freq
Ni(CO)4 Td Frequency calculation
0 1
- Run the Gaussian program with the file NiCO4f.com (IMPORTANT: it is
necessary to modify the lanza.sge file).

- Check the NiCO4f.log file and use the Gaussview program to

view the calculated frequencies.

- Check the NiCO4f.log file and use the Gaussview program to

view the calculated frequencies.

EXERCISE 3:
Optimize the following compounds
corresponding frequency calculation:

http://www.3dchem.com/3dinorgmolecule.asp?ID=948

and

run

the

http://www.3dchem.com/3dinorgmolecule.asp?ID=979

Optimize the molecules:

Name of the files:

Cr(CO)6
CrCO6

FeCO5

Suggestion:
- Build up the new molecules with Gaussview.

Open a new window

Fe(CO)5
respectively

Select

Select:
octahedral Cr
atom

IMPORTANT!:
Symmetrize the
molecule

Oh = octahedral

- Save the Cr(CO)6

molecule in your terminal
as CrCO6.gjf file.

IMPORTANT
Thick
Write Cartesians

- At CICA: Copy the NiCO4.com file into the CrCO6.com file.

Edit the CrCO6.com file (with the vi editor) and:
- change the name of NiCO4.chk file by CrCO6.chk
- modify the title section
- remove the old coordinates.
- edit the file CrCO6.gfj that has just created (with a text
editor) and copy the cartesian coordinates.
- insert the coordinates into the CrCO6.com file.
- Add the instruction freq to the Route section:
# B3LYP 6-31G* opt freq

(in order to do in a single job both the optimization and

the frequency calculations).
- Save the CrCO6.com file

%mem=1Gb
%nproc=2
%CHK=CrCO6.chk
# B3LYP 6-31G* opt freq

CrCO6.com file

Cr(CO)6 Oh
0 1
Cr
C
C
C
C
C
C
O
O
O
O
O
O

0.00000000
0.00000000
0.00000000
1.90000000
-0.00000000
0.00000000
-1.90000000
0.00000000
-3.01540000
0.00000000
-0.00000000
3.01540000
0.00000000

0.00000000
0.00000000
1.90000000
0.00000000
0.00000000
-1.90000000
0.00000000
0.00000000
0.00000000
3.01540000
0.00000000
0.00000000
-3.01540000

-0.00000000
1.90000000
0.00000000
-0.00000000
-1.90000000
-0.00000000
0.00000000
3.01540000
0.00000000
0.00000000
-3.01540000
-0.00000000
-0.00000000

- For the CrCO6.com file, run the Gaussian program.

IMPORTANT: it is necessary to modify the lanza.sge file.
- Check the corresponding output CrCO6.log file.

- Repeat

the

same procedure for the Fe(CO)5 molecule

(FeCO5.com file).

%mem=1Gb
%nproc=2
%CHK=FeCO5.chk
# B3LYP 6-31G*

FeCO5.com file
opt freq

Fe(CO)5 D3h
0 1
Fe
C
C
C
C
C
O
O
O
O
O

-0.00000000
-1.67142903
0.00000000
0.00000000
1.67142903
-0.00000000
-0.00000000
2.63739377
0.00000000
-0.00000000
-2.63739377

-0.00000000
0.96500000
-1.93000000
-0.00000000
0.96500000
-0.00000000
-0.00000000
1.52270000
-3.04540000
-0.00000000
1.52270000

0.00000000
-0.00000000
-0.00000000
1.93000000
-0.00000000
-1.93000000
3.04540000
0.00000000
0.00000000
-3.04540000
0.00000000

EXERCISE 4:
Draw the following molecular orbitals:

HOMO
HOMO-1
HOMO-2

HOMO
HOMO-1

HOMO
HOMO-1
HOMO-2

Gaussian program

Generation of additional outputs (CICA):

FormCheck file
Transform the checkpoint file in a readable file
> /home/deposito/G03Linda/g03/formchk CrCO6.chk
This generates a new file CrCO6.fchk

- Transfer the CrCO6.fchk file to your terminal and open it with

the Gaussview program.

Open the
MO editor

Select the three

degenerate
HOMO orbitals

Click:
Visualize

Click:
Update

Gaussian Calculations of Simple Organometallic Molecules:

technical aspects
- Introduction
- Practical theoretical chemistry

- Types of complexes to be analyzed

- Gaussian program

- Metal carbonyls

- Input file

- Metal olefin complexes

- Running the calculation

- Information from output

- Theoretical chemistry on paper

Metal carbonyls

Coordination complexes of transition metals with

carbon monoxide. These complexes may be
homoleptic, i.e. contain only CO ligands.

Selected examples:

http://www.3dchem.com/3dinorgmolecule.asp?ID=979
http://www.3dchem.com/3dinorgmolecule.asp?ID=948

http://www.3dchem.com/3dmolecule.asp?ID=96

Simplified MO diagram for CO

Frontier orbitals

Orbital interactions metal-CO

Back donation (also known as the Chatt-Dewar-Duncanson model):

http://goldbook.iupac.org/
A description of the bonding of -conjugated ligands to a transition
metal which involves a synergic process with donation of electrons
from the filled -orbital or lone electron pair orbital of the ligand into
an empty orbital of the metal (donor-acceptor bond), together with
release (back donation) of electrons from an nd orbital of the metal
(which is of -symmetry with respect to the metal-ligand axis) into the
empty *-antibonding orbital of the ligand.

MO diagram of an octahedral compound

Symmetry-adapted
orbitals for an
octahedral complex
ML6

Orbitals of the same

symmetry on the
metal centre

MO diagram of an octahedral compound

MO diagram of an octahedral compound

d orbitals (t2g)

MO diagram of an octahedral compound

-interactions

-donor

-acceptor

MO diagram of an octahedral compound

Perturbation of the d block (in the centre, interactions only) of an

octahedral complex ML6 by the interactions with:
double-face -donor ligands (L = Cl, for example) on the left, and
double-face -acceptor ligands (L = CO, for example) on the right.

MO diagram of an octahedral compound

Cr(CO)6

HOMO

d6

HOMO of Cr(CO)6: t2g orbitals

Outputs from Gaussview

MO diagram of a bpt compound

d-block

MO diagram of a Td compound

d-block

EXERCISE 5:

Optimize the compounds:

[Fe(CO)4(C2H4)]

[Cr(CO)4(C2H4)2]

Name of the files:

FeC2H4CO4

CrC2H42CO4

- Build up the new molecules with Gaussview and prepare

the corresponding input files.

Gaussian Calculations of Simple Organometallic Molecules:

technical aspects
- Introduction
- Practical theoretical chemistry

- Types of complexes to be analyzed

- Gaussian program

- Metal carbonyls

- Input file

- Metal olefin complexes

- Running the calculation

- Information from output

- Theoretical chemistry on paper

Ethylene metal complexes

Selected examples:

[PtCl3(C2H4)]http://www.3dchem.com/3dinorgmolecule.asp?ID=581

[Fe(CO)4(C2H4)]

[Cr(CO)4(C2H4)2]

Ethylene metal complexes

Frontier orbitals for ethylene ligand
E

Orbital interactions metal-ethylene

Ethylene metal complexes

Orbital interactions metal-ethylene

Donation

Back-donation

Ethylene metal complexes

Oh, d6

Ethylene metal complexes

Conformational preferences

Ethylene metal complexes

Interactions between the and * orbitals on ethylene (in the
centre) and the orbitals of the same symmetry on the d6-ML5
fragment in eclipsed (left) and staggered (right) conformations.

Ethylene metal complexes

Construction of the MO for the eclipsed (left) and staggered (right)
conformations of the d6-[ML5(2-ethylene)] complex, by interaction
between the and * orbitals on ethylene (centre) and the orbitals of the
d6-ML5 fragment.

Ethylene metal complexes

Conformational preferences

Ethylene metal complexes

Comparison of the back-donation interactions (d*) in the
perpendicular (on the left) and coplanar (on the right) conformations of
a d8-[ML4(2-ethylene)] complex. The energy levels and symmetries of
the d orbitals involved are given in the centre of the diagram.

Ethylene metal complexes

Conformational preferences

Ethylene metal complexes

Diagram for the interaction between the nonbonding d orbitals (in the
centre) and the * orbitals on the ethylene ligands in the coplanar (D2h, on
the left) and perpendicular (D2d, on the right) conformations of an
octahedral trans-[ML4(2-C2H4)2] complex with a d6 electronic configuration.