Homogeneous Catalysis : Mechanisms and Industrial Applications

by Bhaduri, Sumit; Mukesh, Doble

• ISBN13: 9780471372219
• ISBN10: 0471372218
• Edition: 1st
• Format: Hardcover
• Copyright: 2000-03-13
• Publisher: Wiley-Interscience

Summary

Problems of variable complexities accompanying each chapter.

Author Biography

SUMIT BHADURI, PhD, is a visiting professor at Northwestern University, Evanston, Illinois, and head of research for Reliance Industries Limited, Indias largest private sector company. <p> DOBLE MUKESH, PhD, is Senior Scientist with ICI India R & T Center, Thane, India.

Table of Contents

Preface	xiii
Chemical Industry and Homogeneous Catalysis	1	(12)
Feed Stocks and Definitions	1	(1)
Feed Stock to Basic Building Blocks by Heterogeneous Catalysis	2	(2)
Basic Building Blocks to Downstream Products by Homogeneous Catalysis	4	(1)
Comparison Among Different Types of Catalysis	5	(3)
What Is To Follow---A Summary	8	(5)
Problems	10	(1)
Bibliography	11	(2)
Basic Chemical Concepts	13	(24)
The Metal	13	(4)
Oxidation State and Electron Count	13	(2)
Coordinative Unsaturation	15	(2)
Rare Earth Metals	17	(1)
Important Properties of Ligands	17	(2)
CO, R2C=CR2, PR3, and H- as Ligands	17	(1)
Alkyl, Allyl, and Alkylidene Ligands	18	(1)
Important Reaction Types	19	(6)
Oxidative Addition and Reductive Elimination	19	(3)
Insertion Reactions	22	(1)
β-Hydride Elimination	23	(1)
Nucleophilic Attack on a Coordinated Ligand	23	(2)
Energy Considerations---Thermodynamics and Kinetics	25	(1)
Catalytic Cycle and Intermediates	25	(12)
Kinetic Studies	28	(1)
Spectroscopic Studies	29	(1)
Model Compounds and Theoretical Calculations	30	(3)
Problems	33	(2)
Bibliography	35	(2)
Chemcal Engineering Fundamentals	37	(18)
Reactor Design	37	(6)
Stirred Tank Reactors	39	(2)
Tubular Reactors	41	(1)
Membrane Reactors	42	(1)
Construction Materials	43	(1)
Operating Conditions	43	(1)
Mass Transfer in Multiphase Reactions	44	(1)
Heat Transfer	45	(1)
Catalyst Recovery	46	(1)
Unit Operations	47	(3)
Crystallization and Filtration	47	(1)
Distillation	47	(2)
Liquid-Liquid Extraction	49	(1)
Gas--Liquid Absorption (or Scrubbing)	50	(1)
Safety Aspects	50	(1)
Effuent and Waste Disposal	51	(1)
Economics	51	(4)
Problems	52	(2)
Bibliography	54	(1)
Carbonylation	55	(30)
Introduction	55	(1)
Manufacture of Acetic Acid	56	(6)
The Monsanto Process---The Catalytic Cycle	56	(3)
Mechanistic Studies and Model Compounds	59	(1)
The BASF Process---The Catalytic Cycle	60	(1)
BASF Process---Mechanistic Studies	61	(1)
Water-Gas Shift Reaction and Rhodium-Catalyzed Carbonylation	62	(2)
Fischer-Tropsch Reaction and Cobalt-Catalyzed Carbonylation	64	(2)
Rhodium-Catalyzed Carbonylation of Other Alcohols	66	(2)
Carbonylation of Methyl Acetate	68	(2)
Mechanism and Catalytic Cycle	69	(1)
Carbonylation of Alkynes; Manufacture of Methyl Methacrylate	70	(4)
Mechanism and Catalytic Cycle	71	(3)
Other Carbonylation and Hydrocarboxylation Reactions	74	(3)
Engineering Aspects	77	(8)
Problems	79	(3)
Bibliography	82	(3)
Hydroformylation	85	(20)
Background	85	(1)
The Rhodium Process	86	(10)
The Catalytic Cycle	86	(2)
Product Selectivity	88	(1)
Mechanistic Studies	88	(2)
The Phosphorus Ligands and Selectivity	90	(2)
Water-Soluble Phosphines and Rhodium Recovery	92	(3)
Catalyst and Ligand Degradation	95	(1)
Cobalt-Based Hydroformylation	96	(2)
Other Hydroformylation Reactions	98	(1)
Engineering Aspects	99	(6)
Problems	99	(3)
Bibliography	102	(3)
Polymerization	105	(28)
Introduction	105	(2)
Polyethylene	105	(1)
Polypropylene	106	(1)
Catalysts for Polyethlene	107	(1)
Catalysts for Polypropylene	108	(1)
Catalytic Cycle for Alkene Polymerization	109	(4)
Cossee--Arlman Mechanism	109	(2)
Mechanism of Alkene Insertion	111	(2)
Mechanistic Evidence	113	(1)
Metallocene Catalysts	113	(10)
Structures of Metallocene Catalysts and the Co-catalysts	114	(4)
Special Features and Advantages of Metallocene Catalysts	118	(1)
Mechanism of Polymerization and Stereocontrol by Metallocene Catalysts	119	(4)
Chromocene and Heterogeneous Catalysts	123	(2)
Polymers of Other Alkenes	125	(1)
Engineering Aspects	125	(8)
Problems	127	(3)
Bibliography	130	(3)
Other Alkene-Based Homogeneous Catalytic Reactions	133	(38)
Introduction	133	(1)
Isomerization of Alkenes	133	(2)
Catalytic Cycle	134	(1)
Hydrogenation of Alkenes	135	(3)
Catalytic Cycle	136	(1)
Mechanistic Evidence	137	(1)
Oligomerization of Ethylene	138	(4)
Shell Higher Olefin Process	139	(3)
Di-, Tri-, and Codimerization Reactions	142	(5)
Dimerization of Propylene	142	(1)
Di- and Trimerization of Butadiene	142	(5)
Dimerization of Butadiene with Ethylene	147	(1)
Metathesis Reactions	147	(4)
Mechanistic Studies	147	(4)
Hydrocyanation	151	(8)
Catalysts for Hydrocyanation	153	(1)
Catalytic Cycle for the First Stage	154	(2)
Catalytic Cycle for the Second Stage	156	(3)
Hydrosilylation	159	(2)
Catalytic Cycle and Mechanism	160	(1)
C--C Coupling and Cyclopropanation Reactions	161	(10)
Catalytic Cycle for the Heck Reaction	163	(1)
Catalytic Cycle for Cyclopropanation	163	(2)
Problems	165	(3)
Bibliography	168	(3)
Oxdation	171	(24)
Introduction	171	(1)
Wacker Oxidation	172	(4)
The Background Chemistry	173	(1)
Catalytic Cycle and Mechanism	174	(2)
Metal-Catalyzed Liquid-Phase Autoxidation	176	(6)
Mechanism of Autoxidation	177	(2)
Special Features of Cyclohexane Oxidation	179	(2)
Special Features of p-Xylene Oxidation	181	(1)
Polymers (Polyesters and Polyamides) from Autoxidation Products	182	(1)
Epoxidation of Propylene	183	(3)
Catalytic Cycle and the Mechanism of Propylene Epoxidation	184	(2)
Oxo Complexes as Homogeneous Oxidation Catalysts	186	(2)
Mechanism of Oxidation by Oxo Compounds	187	(1)
Engineering and Safety Considerations	188	(7)
Problems	190	(3)
Bibliography	193	(2)
Asymmetric Catalysis	195	(38)
Introduction	195	(1)
General Features of Chiral Ligands and Complexes	196	(6)
Mechanisms and Catalytic Cycles	202	(13)
Mechanism of Asymmetric Hydrogenation	203	(4)
Asymmetric Isomerization and Mechanism	207	(2)
Asymmetric Epoxidation of Allylic Alcohols and Mechanisms	209	(2)
Asymmetric Epoxidation of Alkenes other than Allyl Alcohols	211	(1)
Asymmetric Hydrolysis of Epoxides	212	(3)
Asymmetric Dihydroxylation Reaction	215	(2)
Mechanism of ADH Reaction	216	(1)
Asymmetric Catalytic Reactions of C--C Bond Formation	217	(16)
Asymmetric Hydroformylation Reaction	218	(3)
Mechanism of Asymmetric Hydroformylation Reaction	221	(2)
Asymmetric Hydrocyanation Reaction	223	(2)
Nitroaldol Condensation	225	(2)
Problems	227	(4)
Bibliography	231	(2)
Index	233