Simulation of Catalytic Processes

(Homogeneous Catalysis)
Basic Concepts in Organometallic Chemistry Gregori Ujaque

Master en Qumica Terica i Computacional, curs 08-09

SCP

Basic Concepts in Organometallic Chemistry

Outline

Introduction Types of Metal Ligand Bonds Oxidation state Electron Counting 18e- Rule Coordination Geometries

2008-09

SCP

Introduction
Homogeneous catalysis based on Transition Metal Complexes Organometallic Complexes Organometallic complexes characterize the catalytic cycles Computational Organometallic Chemistry is a highly useful tool for analyzing catalytic cyles

2008-09

SCP

Introduction
Computational Organometallic Chemistry Bridging the gap between theoretical and experimental languages Simple and fundamental concepts always present in the language of organometallic chemists (all chemists !!)

2008-09

SCP

Introduction
Computational Challenges:
- large number of orbitals (many of them core)

METALS

- electron-correlation problems (dynamic and non-dynamic) - relativistic effects (heaviest metals)

LIGANDS

- large size: number of atoms, AO - conformational possibilities

2008-09

SCP

Basic Concepts in Organometallic Chemistry

Transition Metal Complexes Metal Ligand Interactions

Hapticity Denticity (chelating complexes) Types of M L Bond

Oxidation State 18-electron Rule Coordination Geometries

2008-09

SCP

Metal Ligand Interactions

1.1. Hapticity: refers to the number of contiguous atoms from a ligand coordinated to the metal center ():
M 4

These structures may be represented in different ways:

2008-09

SCP

Metal Ligand Interactions

1.2. Denticity: refers to the number of atoms in a single ligands that bind to a central metal in a coordination complex (), chelating complexes:
- Monodentate (1):

- Bidentate (2): . . . - Hexadentate (6):

(EDTA)

2008-09

SCP

Metal Ligand Interactions

1.3. Isomerism of the ligand: same ligand different coordination types Ex.
allyl

M 2

M 4

butadiene

Cyclopentadienyl Cp

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: d orbitals

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -Bonds

M
empty d orbital filled orbital (lone pair)

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -Bonds Examples:

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding -Bonds

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding -Bonds

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding MO diagram

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding -Bonds Examples: M-Alkenes:

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding -Bonds

M-Alkynes:

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding -Bonds with alkynes

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: Backbonding -Bonds Examples:

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -bond complexes

X M
empty d orbital filled -bond (bonding e-)

M X

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -bond complexes MO Diagram

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -bond complexes Examples:
Kubas complex

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -bond complexes: agostic complexes

Y M
empty d orbital filled -bond (bonding e-)

M X
belongs to a bonded ligand

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -bond complexes: agostic complexes
H C LnM
Agostic interaction

H X LnM
General agostic interaction

H X LnM
-d interaction

H C LnM
Agostic distortion

2008-09

SCP

Metal Ligand Interactions

Types of Metal Ligand Bonds: -bond complexes: agostic complexes

2008-09

SCP

Periodic Table Trends

Early Transition Metals Low electronegativities Higher oxidation states
d 21 d 22 d 23 24 d d 25

Late Transition Metals Higher electronegativities Lower oxidation states

d 26 d 27 d 28 d s 29

Sc Ti
Scandium Titanium

V
Vanadium

Cr
Chromium

Mn Fe Co Ni Cu
Manganese Iron Cobalt Nickel Copper

39

40

41

42

43

44

45

46

47

Y
Yttrium

Zr
Zirconium

Nb Mo Tc Ru Rh Pd Ag
Niobium Molybdenum Technetium Ruthenum Rhodium Palladium Silver

57

72

73

74

75

76

77

78

79

La Hf Ta W
Lanthanum Hafnium Tantalum Tungsten

Re Os Ir
Rhenium Osmium Iridium

Pt Au
Platinum Gold

EARLY

LATE
2008-09

SCP

Periodic Table Trends

Ligands
SOFT nucleophile HARD nuclephile

Metal Centers
HARD electrophile SOFT electrophile

EARLY

LATE

2008-09

SCP

Periodic Table Trends

HARD
Hard nucleophiles (ligand) Have a low energy HOMO with high charge density (negative charge) Hard electrophiles (metal) Have a high energy LUMO with high charge density (positive charge) Hard (L) Hard (M) interaction: is predominantly ionic in character. It is favourable because of strong Coulombic attraction

SOFT
Soft nucleophiles (ligand) Have a high energy HOMO with low charge density Soft electrophiles (metal) Have a low energy LUMO with low charge density Soft (L) Soft (M) Is predominantly covalent in character. It is favourable because of small E between the HOMO of the ligand and the LUMO of the metal (EM-EL)

Fleming Frontier Orbitals and Organic Chemical Reactions, 1976.

2008-09

SCP

Electron Counting
Corresponds to the formal distribution of the electrons in the complex: Metal: dn electronic configuration - Oxidation state Ligands: Hapticity and denticity should be taken into
account: Neutral ligands:

-donors: 2e- for each lone pair Ex. PR3, NR3, CO, etc. -donors: depending on the electrons Ex. 2-R2C=CR2 (2e), 6-C6H6 (6e), 4-C6H6 (4e)

Anionic ligands (ionic model):

Ex. H-, Cl-, CH3-, SR-, O2-, 5-C5H5 (Cp) (6e-)

2008-09

SCP

Electron Counting
Metal: dn electronic configuration - Oxidation state
Number of valence electrons (ve) of TM atoms: Valence electron configuration for TM: nda(n+1)sb (n = 3, 4, 5) Valence electrons of the metal atom: a+b = ve

ve

2008-09

SCP

Electron Counting
Metal: dn electronic configuration - Oxidation state
Number of valence electrons (ve) of TM atoms: Valence electron configuration for TM: nda(n+1)sb (n = 3, 4, 5) Valence electrons of the metal atom: a+b = ve
d3 21 d4 22 d5 23 24 d6 d7 25 d8 26 d9 27 d 10 28 d 10s 1 29

Sc Ti
Scandium Titanium

V
Vanadium

Cr
Chromium

Mn Fe Co Ni Cu
Manganese Iron Cobalt Nickel Copper

39

40

41

42

43

44

45

46

47

Y
Yttrium

Zr
Zirconium

Nb Mo Tc Ru Rh Pd Ag
Niobium Molybdenum Technetium Ruthenum Rhodium Palladium Silver

57

72

73

74

75

76

77

78

79

La Hf Ta W
Lanthanum Hafnium Tantalum Tungsten

Re Os Ir
Rhenium Osmium Iridium

Pt Au
Platinum Gold

2008-09

SCP

Electron Counting
Metal: dn electronic configuration - Oxidation state
Oxidation state (os): degree of oxidation of the metal (formal charge) In order to determine the oxidation state of the metal in the complex, one performs a fictitious dissociation of all the ligands, supposing that each of them, either L (neutral) or X (anionic), takes with it the electron pair that created the metalligand bond (x). The remaining charge on the metal after this decomposition, taking into account the charge of the complex (q), is the oxidation state of the metal in the complex.

os = x + q

2008-09

SCP

Electron Counting
Metal: dn electronic configuration - Oxidation state
Formal number of electrons remaining in the metal (n):

n = ve os
ve = valence electrons os = oxidation state Metal electronic configuration in the complex:

dn

Example: Fe (group 8, period 4) valence electron configuration: 3d64s2=> 8 valence electrons Fe(0) =>d8 Fe(II) =>d6 Fe(III) =>d5 Fe(IV) =>d4

2008-09

SCP

Electron Counting
Ligand electron counting: -donors

2008-09

SCP

Electron Counting
Examples

2008-09

SCP

18 e- Rule
A TM tends to have 18 valence electrons
(analogy with the octet rule for main group elements)

2008-09

SCP

18 e- Rule
A TM tends to have 18 valence electrons
(Octahedral case)
px p y s pz p z px py s dx2 -y 2 dz 2

*
LUMO (lowest unoccupied molecular orbital)

Metal d Orbitals

HOMO (highest occupied molecular orbital)

Ligand Orbitals

M-L bonding Orbitals

2008-09

SCP

18 e- Rule

2008-09

SCP

Basic Concepts in Organometallic Chemistry

Outline

Introduction Types of Metal Ligand Bonds Oxidation state Electron Counting 18e- Rule Coordination Geometries

2008-09

SCP

Coordination Geometries
Large metals and small ligands lead to high coordination numbers, e.g. [Mo(CN)8]4-. Small metals with large ligands lead to low coordination numbers, e.g. Pt[P(CMe3)]2+. Due to their large size, lanthanides, actinides and early transition metals tend to have high coordination numbers.

2008-09

SCP

Coordination Geometries
Two-coordination
linear

Three-coordination

Trigonal Planar
2008-09

SCP

Coordination Geometries
Four-coordination

square-planar

tetrahedral

Five-coordination

Trigonal bipyramidal

Square pyramidal
2008-09

SCP

Coordination Geometries
Six-coordination

trigonal prismatic

octahedral

Seven-coordination

pentagonal bipyramidal
2008-09

SCP

Basic Concepts in Organometallic Chemistry

Outline

Introduction Types of Metal Ligand Bonds Oxidation state Electron Counting 18e- Rule Coordination Geometries

2008-09

SCP

Basic concepts in organometallic chemistry Computational Organometallic Chemistry Elementary steps in Homogeneous Catalysis

Simulation of Homogeneous Catalytic Processes

2008-09

SCP

The End

2008-09