66286 - Metallorganic Chemistry

Learning outcomes

At the end of the course, the students know the principles and main properties of organometallic compounds. They are able to understand the role of organometallic compounds in modern industrial catalytic processes. They know how to design the synthesis of these compounds and use the most suitable spectroscopic techniques for their characterization.

Course contents

Prerequisites:

The student must possess a good knowledge of coordination chemistry and molecular orbital theory.

Program:

Module 1 (Prof. Grepioni): 4 ECTS credits, corresponding to 32 hours of lectures.

Module 2 (Prof. Parisini): 2 ECTS credits, divided into 1 ECTS for exercises (12 hours) and 1 ECTS for laboratory work (12 hours), comprising introductory lessons to the laboratories.

The two modules will not be held as two separate time blocks: lectures, exercises, and laboratory sessions will alternate to allow for a better understanding of the course topics.

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MODULE 1

• Introduction to the course and to Modules 1 and 2.
•  Review of concepts in coordination chemistry. Types of bonds and ligands.
• Organometallic chemistry. The 18-electron rule and its limitations. The concept of oxidation state and its limitations. Methods for predicting the stability of an organometallic complex.
• Complexes with sigma-donor ligands. Metal-alkyl and metal-aryl complexes, hydrides. Sigma complexes. Bond strength.
• Ligand substitution. Metal carbonyls, phosphines, associative and dissociative substitutions, redox substitutions, interchange and photochemical substitutions, effect of counterions and solvents.
• Pi-complexes: alkenes, alkynes, allyl, cyclopentadienyl, metallacycles, arenes.
• Oxidative addition and reductive elimination. Mechanisms and examples.
• Insertion and elimination: types and examples.
• Addition and abstraction: Nucleophilic and electrophilic addition and abstraction.
• Homogeneous catalysis. Catalytic cycles. Alkene hydroformylation. Photoredox catalysis.
• Applications: C–H bond activation.
• Physical characterization methods: brief overview. [Structural characterization via X-ray diffraction is covered in Module 2.]
• Case studies: applications of organometallic chemistry in materials science, industry, and/or environmental fields.
  

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MODULE 2

• Physical characterization methods: theoretical introduction to structural characterization using single crystal X-ray diffraction.
• Diffractometer workshop: hands-on training in the use of a single-crystal diffractometer for molecular structure determination.
• Structural database: introduction to the use of the crystallographic database (CSD)
• Computer-based exercises: use of the crystallographic database for the analysis of molecular and supramolecular structures of organometallic compounds.
• Case studies: practical applications of organometallic chemistry in the fields of materials science, industry, and the environment.
  

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Readings/Bibliography

R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, Wiley-Blackwell, 7th edition, 2019 (or 6th edition, 2014)

The 2014 edition can be read for free at the link:

https://ebookcentral.proquest.com/auth/lib/unibo/ [Ebook Central UniBO]

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Slides (to be used as a reference) will be upload in VLE just before each lecture. The lecture slides will contain explicit indications of the textbook chapters to refer to for the individual study.

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Other texts:

C. Elschenbroich, Organometallics, Wiley-VCH, 2006.G.O. Spessard,

G. L. Miessler, Organometallic Chemistry, Oxford University Press, terza edizione, 2015

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Teaching methods

The course is organized into lectures, computer lab exercises, and instrumental laboratory experiences, during which techniques such as single-crystal X-ray diffraction and molecular visualization software are used.

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Activities in the chemical laboratory are part of the course. In order to participate in lab experiences, all students must have attended health and safety Modules 1 and 2 [e-learning mode at https://www.unibo.it/it/servizi-e-opportunita/salute-e-assistenza/salute-e-sicurezza/sicurezza-e-salute-nei-luoghi-di-studio-e-tirocinio] and (for the X-ray diffraction laboratory) Module 3 [in presence]. Information about Module 3 dates and locations will be published in the course website. 

Assessment methods

The exam is oral and lasts 40–45 minutes:

The first question will consist of a discussion of a short scientific article, indicated in class, and whose references will be uploaded to VLE at the end of the course.

An exercise may also be proposed, taken from those at the end of the chapters in the recommended textbook (Crabtree), and discussed during the course.

The evaluation will consider the student's ability to:

• present concepts clearly and accurately, both in content and scientific terminology

• connect the acquired knowledge in a way that demonstrates understanding beyond simple memorization of the material

The final grade will be a weighted average (based on ECTS credits) of the evaluations for Module 1 and Module 2. Active participation in the exercises and laboratory of module 2 will contribute to the assessment.

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Students with learning disorders and/or temporary or permanent disabilities: please contact the office responsible (https://site.unibo.it/studenti-con-disabilita-e-dsa/en/for-students ) as soon as possible, so they can propose acceptable adjustments.
The request for adaptation must be submitted to the lecturer at least 15 days before the exam date. The lecturer will assess the appropriateness of the adjustments, taking into account the teaching objectives.

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Teaching tools

Projector, PC, white/blackboard. Graphics programs will be used to represent selected molecules.

Office hours

See the website of Fabrizia Grepioni

See the website of Emilio Parisini