66286 - Metallorganic Chemistry

Learning outcomes

Upon completion of the course the student will demonstrate knowledge of the basic principles and main properties of the organometallic compounds. He will be able to understand the role of the organometallic complexes in the modern catalytic industrial processes, plan the synthesis of different classes of organometallic compounds and use advanced methods in characterizing organometallic compounds

Course contents

Prerequisites

The student must have have a good knowledge of inorganic, organic and coordination chemistry.

Program

1 Overview of the principal ligands employed in organometallic compounds. Methods to predict the stability of organometallic complexes (effective atomic number rule, etc.).

2 Organometallic complexes with sigma-donor ligands.

• Synthetic methods to prepare metal-alkyls and metal-aryls complexes

• Factors that control the stability of metal-alkyls complexes. Beta elimination.

3 Complexes with sigma-donor and pi-acceptor ligands.

• Fischer and Schrock carbene complexes . Synthetic methods and reactivity of carbene complexes.

• Metal carbonyls: structure and bonding. Synthesis, structure and reactivity of metal carbonyl complexes.

– metal carbonyl complexes containing single or multiple metal-metal bonds: transition metal carbonyl clusters. Geometries of the metal polyhedra. Electron counting rule for TM carbonyl clusters.

4 Complexes with sigma and pi donor/pi acceptor.

• Synthesis, structure and reactivity of alkene complexes.

• Synthesis, structure and reactivity of di- and polyolefinic complexes.

• Synthesis, structure and reactivity of alkyne complexes

• Enyl complexes. Structure and bonding of allyl complexes.

• Cyclopentadienyl complexes. Metallocenes. Synthesis, structure and reactivity of metallocenes.

• Arene complexes. Reactivity of arene complexes.

5 Main reactions in organometallic compounds

• Reactions of oxidative addition and reductive elimination

• Substitution reactions at square planar metal complexes

• Insertion and elimination (deinsertion) reactions

• Nucleophilic addition at coordinated ligands

6 Physical methods in organometallic chemistry for the determination of the molecular structure.

• Single crystal and powder X-ray diffraction (introductory level)

• ¹H, ¹³C and ³¹P NMR spectroscopy.

7 Organometallic catalysis:

• Examples of the use of organometallic catalyst in the organic synthesis

• Oligomerization and polymerization catalyzed by organometallic complexes.

During the term a few articles in the field of organometallic chemistry will be distributed to the students.

Readings/Bibliography

C. Elschenbroich, Organometallics, Wiley-VCH, 2006.

R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, Wiley-Blackwell, 2009.

G.O. Spessard, G. L. Miessler, Organometallic Chemistry, Oxford University Press, third edition, 2015

Teaching methods

The course is organized in lectures and laboratory experiments in which the use of X-ray diffraction techniques is shown. In view of the type of activity and teaching methods adopted, students are required to attend Module 1 and 2 in e- learning mode [https://www.unibo.it/it/servizi-e-opportunita/salute-e-assistenza/salute-e-sicurezza/sicurezza-e-salute-nei-luoghi-di-studio-e-tirocinio]

Assessment methods

Oral exam on the topics discussed in the course.

Teaching tools

overhead projector, pc, blackboard.

Office hours

See the website of Magda Monari