Study guide

Instructional Offering:

Code:

Lecturer:

Prescribed Textbook:

Inorganic Chemistry IV

Module 2

Organometallic and Industrial Chemistry

CHI4112

Prof B Zeelie

None

Recommended reading:

BOOK

Powell, "Principles of Organometallic Chemistry", 2nd Ed.

Masters, "Homogeneous Transition Metal Catalysis".

Büchner, Schlibs, Winter, Büchel, "Industrial Inorganic Chemistry".

CODE

P

M

BSWB

Contents

General

Functions of this guide

General information and regulations

Course layout

Attendance

Tests and tutorials

Practical component

Class mark

Examination

Pass requirements

Unit 1: Organometallic Chemistry

Lecture hours

Unit Content

Study Objectives

Unit 2: Homogeneous Catalysis

Lecture hours

Unit Content

Study Objectives

Unit 3: Industrial Inorganic Chemistry

Lecture hours

Course Content

Study Objectives

1. GENERAL

There is no single prescribed textbook and you will be provided with comprehensive notes on the relevant subject matter. However, you may consult the above list of reference books for further information. Remember, what we do as lecturers will enable you to obtain your diploma; what you do will make you a chemist.

Reference books may be obtained from the library and/or from your lecturer.

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2. FUNCTIONS OF THIS GUIDE

To assist you in the interpretation of the syllabus

To break down the syllabus into smaller units

To highlight essential learning material

To enable you to evaluate your own progress

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3. GENERAL INFORMATION AND REGULATIONS

3.1 Course layout

The module "Organometallic and Industrial Chemistry" is divided into three units, namely:

Unit 1 Organometallic Chemistry

Unit 2 Homogeneous Catalysis

Unit 3 Industrial Chemistry

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3.2 Attendance

You are strongly advised to attend all their lectures as failing to do so will affect the quality of work to be done in tutorials and the ability to answer questions in tests correctly.

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3.3 Tests and tutorials

You will write two (2) major class tests, each of 1.5 hours duration, to evaluate your understanding of the course content. In addition to these tests, you will complete tutorials on a regular basis and write a number of short tutorial tests during the lecture periods. Dates for the class tests and minor tutorial tests will be announced during the lectures.

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3.4 Practical component

The integrated practical which runs throughout the year will be completed during this module and evaluated. The date for submission of the practical report will be announced during the lectures. The mark obtained for the Inorganic Chemistry practical component of the set practicals will be combined with the marks obtained from the two class tests as shown in § 3.5 below.

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3.5 Class mark

Class marks are determined from the marks obtained in the two class tests and the minor tutorial tests in the following ratio:

Class Test 1:

Class Test 2:

Minor tests:

Prelim class mark

Prelim class mark

Practical

Class Mark:
331/3%
331/3%

331/3%

100%

70%

30%

100%

Note that in order to obtain examination entrance, you must achieve a minimum of 40% for your class mark. See exam admission requirements. Also note the rules and regulations regarding writing and missing class tests in the Department’s Rules and Regulations Brochure.

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3.5 Examination

The final examination for this module will consist of one three (3) hour written examination. The paper will be divided into the following sections:

Section A: Organometallics and Catalysis

Section B: Industrial Chemistry

Both sections must be answered. The mark allocation for each section in the examination paper is proportional to the number of lectures allocated to each section.

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3.6 Pass requirements

3.6.1 Modules

You will obtain a pass for a module if the combined class and examination mark is 50%, or more, provided that a subminimum of 40% has been obtained in the final examination. The combined mark for each module is computed as follows:

Class mark :

Exam mark :

Final mark :
40%
60%

100%

3.6.2 Course

The final course mark for Inorganic Chemistry IV is calculated as a weighted average of the marks obtained for the individual modules, "Theoretical Inorganic Chemistry" and "Organometallic and Industrial Chemistry". Should you fail one of the modules, you retain your pass mark for other modules passed. You will pass the course Inorganic Chemistry IV only if a final mark of at least 50% is obtained for each module. See Calculating the final mark.

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4. UNIT 1 ORGANOMETALLIC CHEMISTRY

4.1 Lecture hours

7 × 1 hr = 7 hrs

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4.2 Unit Content

4.2.1 General survey:

! Introduction

! Properties

! Classification

! Stability

4.2.2 Methods of formation - Main group elements:

! Metal and organic halogen

! Metal exchange

! Organometallic compounds and metal halides

! Metal hydrides with alkenes and alkynes

! Insertion reactions

! From diazo compounds

! Decarboxylations

4.2.3 Some transition metal chemistry relevant to organometallic chemistry:

! The 18 electron rule

! Transition metal carbonyls

! Classification of ligands

! Molecular orbital theory

! General reactions of transition metal complexes

4.2.4 Organotransition metal chemistry:

! Complexes of alkenes and alkynes

! Allyl and diene complexes

! Five electron ligands

! Complexes of arenes

P 1-13

P 15-28

P 148-211

P 213-249

P 253-263

P 278-292

P 311-320

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4.3 Study Objectives

After completion of this unit you should be able to:

P mention and discuss the factors which will favour the formation of ionic organometallic compounds;

P discuss the stability of organometallic compounds w.r.t. (i) hydrolysis and (ii) oxidation;

P compare the variation in M-C bondstrengths in the main block elements and the d-block elements;

P explain why many organometallic compounds may be isolated in spite of the fact that they may be thermodynamically unstable;

P explain the decomposition of organometallic compounds by $-hydrogen transfer;

P use MO-theory to rationalize the applicability of the EAN rule to organometallic compounds;

P determine the number of valence electrons in organometallic compounds;

P discuss the bonding in linear M-CO groups;

P mention and illustrate the two main methods used for the preparation of carbonyl compounds;

P mention and illustrate the two main reactions of metal carbonyls;

P explain how one can distinguish between a terminal and a bridging carbonyl in a polynuclear compound;

P deduce the relative strengths of M-C interaction in carbonyl compounds using i.r. stretching frequencies;

P explain how metals with odd e⁾ numbers can obey the EAN rule;

P explain the variation in M-CO bondstrengths in the d-block elements;

P discuss the substitution of CO from metal complexes with respect to:

± mechanism, and

± extent of reaction;

P discuss the bonding between ethylene and a metal ion using:

± a simple MO-representation, and

± a valence bond representation;

P illustrate the two possible bonding modes between a metal ion and 1,3 butadiene and explain how the C-C bondlengths in the diene group can infer the mode of bonding.

P predict structural properties of ML₁L₂ (butadiene) complexes;

P explain what is meant by the terms "cyclopentadienyl compound" and "cyclopentadienide compound";

P explain how ferrocene can be synthesized (different methods);

P give a qualitative description of the bonding in ferrocene;

P present some evidence in favour of the proposition that manganocene is thought to be largely ionic;

P discuss the bonding in BeCp₂;

P discuss the bonding between metals and alkynes;

P explain why the allyl group, CH₂ = CH - CH₂, can behave as a monohapto or a trihapto ligand.

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5. UNIT 2 HOMOGENEOUS CATALYSIS

5.1 Lecture hours

5 × 1 hr = 5 hrs

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5.2 Unit Content

5.2.1 General:

! Basic principles

! Transition metals in catalysis

! Homo- versus heterogeneous catalysis

! Molecule activation

! Proximity interaction

! The catalytic cycle

5.2.2 Homogeneous catalyst systems in operation:

! Hydrogenation

! Isomerization

! Carbonylation

! Hydroformylation

M 1-35

M 38-196

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5.3 Study Objectives

After completion of this unit you should be able to:

P state the two postulates of the 16/18 e⁾ rule;

P give the five main organometallic reactions and state how each may be identified;

P discuss various definitions of a catalyst;

P use thermodynamic data to predict the feasibility of reactions;

P discuss catalysis by transition metals i.t.o.:

± bonding ability,

± choice of ligands,

± ligand effects,

± variable oxidation state, and

± variable of coordination number;

P compare homogeneous and heterogeneous catalysis;

P discuss activation of molecules: ± by coordination,

± by addition;

P define and explain: ± oxidative addition,

± homolytic addition,

± heterolytic addition;

P explain the terms: ± proximity interaction,

± insertion/inter-ligand migration,

± elimination;

P state the 16/18 electron rule as pertaining to catalysis;

P discuss fully the hydrogenation of alkenes using Wilkensons catalyst;

P discuss alkene isomerization by: ± metal-alkyl intermediates,

± metal-allyl intermediates;

P discuss the synthesis of acetic acid from methanol;

P define the term hydroformylation;

P discuss hydroformylation reactions using rhodium catalysts.

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6. UNIT 3 INDUSTRIAL CHEMISTRY

6.1 Lecture hours

2 × 1 hr = 2 hrs

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6.2 Unit Content

6.2.1 Industrial Inorganic Chemistry:

! Chromium

! Manganese

BSWB 255-268

BSWB 277-287

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6.3 Study Objectives

After completion of this unit the student should be able to:

P discuss the economic importance of chromium;

P discuss the synthesis of:

± alkali chromates,

± sodium dichromate,

± chromium oxides;

P discuss the economic importance of manganese;

P discuss the synthesis of:

± manganese(II) oxide,

± manganese(IV) oxide,

± potassium permanganate.

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Study guide

Contents

1. GENERAL

2. FUNCTIONS OF THIS GUIDE

3. GENERAL INFORMATION AND REGULATIONS

3.1 Course layout

3.2 Attendance

3.3 Tests and tutorials

3.4 Practical component

3.5 Class mark

3.5 Examination

3.6 Pass requirements

4. UNIT 1 ORGANOMETALLIC CHEMISTRY

4.1 Lecture hours

4.2 Unit Content

4.2.1 General survey:

4.2.2 Methods of formation - Main group elements:

4.2.3 Some transition metal chemistry relevant to organometallic chemistry:

4.2.4 Organotransition metal chemistry:

P 1-13

P 15-28

P 148-211

4.3 Study Objectives

5. UNIT 2 HOMOGENEOUS CATALYSIS

5.1 Lecture hours

5.2 Unit Content

5.2.1 General:

5.2.2 Homogeneous catalyst systems in operation:

M 1-35

5.3 Study Objectives

6. UNIT 3 INDUSTRIAL CHEMISTRY

6.1 Lecture hours

6.2 Unit Content

6.2.1 Industrial Inorganic Chemistry:

6.3 Study Objectives