ORGANOMETALLIC CHEMISTRY

The course belongs to the area of specialized chemical disciplines and its aim is to provide to students an in-depth knowledge of organometallic chemistry of transition elements.
The formative objectives of the course are: 1) to highlight the peculiarity of metal-carbon bond and the consequent capability of the metallic centre to activate specific reaction of the organic fragment; 2) to classify and describe the features of the organometallic compounds in reference to both metallic centre and organic fragment; 3) to become acquainted with the main classes of reaction of organometallic compounds; 4) to show the important applications of organometallic compounds of transition metals in homogeneous catalysis and more generally in organic synthesis and in sustainable processes.

1. Knowledge and comprehension:
A) to be familiar with the main classes of organometallic compounds and the role played by metallic centre and organic fragment;
B) to be familiar with the typical reaction of organometallic chemistry (oxidative addition and reductive elimination, insertion on metal-carbon bond, attack on coordinate ligand, transmetalation etc..)

2. Ability to apply knowledge and comprehension:
A) to be able to utilize the knowledge of the features of an organometallic compounds to predict its reactivity;
B) to use the knowledge of coordination and organometallic chemistry to develop protocols for the synthesis of organometallic compounds,
C) to be able to plan the use of the organometallic compounds in a catalytic processes possibly sustainable.

3. Ability of judgment:
A) to be able to recognize possible errors by a critical analysis of applied procedure;
B) to be able to understand and properly interpret the information reported in the articles of the most important journals of organometallic chemistry.

4. Ability of exposition:
A) to be able to communicate acquired knowledge and the results of its application using an appropriate terminology both orally and in written form;
B) to be able to interact with the docent and other students during the lesson.

5. Ability of learning:
A) to be able to take notes, selecting information in order of importance and priority;
B) to be sufficiently autonomous in the resolution of problems of organometallic chemistry.

to have attended the course of Chemistry of transition metal and laboratory (CM0315).

The contents of the course can be divided in two main sections:

First section : The organometallic compounds
Formative objectives: (1) and (2) Expected results of learning 1A, 2A, 2B, 3A, 3B 4A, 4B, 5A, 5B
The organometallic compounds:
General properties of Organometallic complexes: the 18-Electron rules and its limitations. Electron counting. Oxidation state. Coordination number and geometry. The concept of back-bonding; Effects of Complexation and main types of ligands.
Metal carbon bonds: The stability of transition metal alkyls; the preparation of Metal alkyls: Characterization and properties of metal-alkyls; Alkene and Alkyne complexes ; Allyl compounds; Diene complexes; Cyclopentadienyl compounds; Arene complexes; Metal carbenes.

Second section : The organometallic reactions
Formative objectives: (3) and (4) Expected results of learning 1B, 2C, 3A, 3B 4A, 4B, 5A, 5B
Oxidative Addition and Reductive Elimination: oxidative adition with concerted mechanism; SN2 mechanism; radical mechanisms; ionic mechanisms; reductive elimination mechanisms; oxidative coupling.
Insertion and Elimination: reactions involving CO; reactions involving alkenes; reactions involving SO2; alfa and beta elimination.
Nucleophilic and electrophilic addition: nucleophilic addition to CO; nucleophilic addition to polyene and polyenyl ligands; nucleophilic abstraction; electrophilic attack mechanisms; electrophilic abstraction.
Organometallic catalysis and sustainable processes with particular reference to sustainable processes.

Lectures notes.
“The Organometallic Chemistry of the Transition Elements”, R.H. Crabtree, IIIrd ed., Wiley.
"Organotransition Metal Chemistry" J. F. Hartwig, Univ. Science Books, Mill Valley, California

The oral examination consists in a series of questions regarding the part of the program reported in the section “ Contents”. The student will be able to show both the learning of program subjects and the ability to expose them in formal manner.
In particular it will be requested the capability of describing the features, reactivity and method of synthesis of a submitted organometallic compound.
In more detail, the method by which the final mark of the exam will be assigned will be defined as follows:
A. Scores in the range of 18-22 will be assigned in the presence of:
• sufficient knowledge and applied comprehension regarding the program;
• limited ability to gather and/or interpret data, forming independent judgments;
• sufficient communication skills, especially in relation to the use of specific language.
B. Scores in the range of 23-26 will be assigned in the presence of:
• decent knowledge and applied comprehension regarding the program;
• decent ability to gather and/or interpret data, forming independent judgments;
• decent communication skills, especially in relation to the use of specific language.
C. Scores in the range of 27-30 will be assigned in the presence of:
• good or excellent knowledge and applied comprehension regarding the program;
• good or excellent ability to gather and/or interpret data, forming independent judgments;
• fully appropriate communication skills, especially in relation to the use of specific language.
D. The “lode” will be awarded in the presence of excellent knowledge, applied comprehension regarding the program, judgment skills, and communication abilities.

Frontal lesson with support of slides. The slides will be provide to students in electronic format.

Italian

Accessibility, Disability and Inclusion
Accommodation and support services for students with disabilities and students with specific learning impairments:
Ca’ Foscari abides by Italian Law (Law 17/1999; Law 170/2010) regarding support
services and accommodation available to students with disabilities. This includes students with mobility, visual, hearing and other disabilities (Law 17/1999), and specific learning impairments (Law 170/2010). In the case of disability or impairment that requires accommodations (i.e., alternate testing, readers, note takers or interpreters) please contact the Disability and Accessibility Offices in Student Services: disabilita@unive.it.
STRUCTURE AND CONTENT OF THE COURSE COULD CHANGE AS A RESULT OF THE COVID-19 EPIDEMIC

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