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Organosilicon Chemistry »

Authors: Brook
ISBN-13: 9780471196587, ISBN-10: 0471196584
Format: Hardcover
Publisher: Wiley, John & Sons, Incorporated
Date Published: December 1999
Edition: (Non-applicable)

Author Biography: Brook

Book Synopsis

A comprehensive, up-to-date reference to synthetic applications of organosilicon chemistry Organic, organometallic, and polymer chemistry as well as materials science all utilize silicon in various forms, yet there is little cross-fertilization of ideas and applications among the disciplines. This book presents a much-needed overview of silicon chemistry, allowing fundamental and applied scientists to take full advantage of progress made within and outside their primary fields of expertise. With an emphasis on the preparation and reactivity of silicon compounds in organic, organometallic, and polymer chemistry, the author examines a broad range of useful topics-from mechanisms to syntheses of and syntheses using different organofunctional silanes. Numerous schemes as well as up-to-date examples from academia and industry will help readers to solve current synthetic problems and explore ideas for future research. Clear, concise coverage includes:
* The mechanistic basis for the development of new silicon-based reactions
* Formation and cleavage of silane reagents and functional siliconheteroatom compounds
* Silicones, silica, polysilanes, and other silicon-containing polymers
* Properties of molecules containing silicon, including bioactivity
* Methods for the preparation of Si-C compounds
* Silicon in organic synthesis
* An extensive functional group index for easy access to functional group transformations

Phillip Magnus

In recent years there have been several books published that describe the various topical uses of silicon in organic synthesis. All of these books have been useful, but they did not present the broader picture of how the chemistry of the element silicon has had a major impact on many technologies. The author refers to some earlier "classical" books on silicon chemistry, particularly Eaborn's text of the 1960s, that set a very high and comprehensive standard by which to be judged. Without a doubt, Michael Brook has met this standard. This book was a pleasure to read. It is very well written in a relaxed and chatty style that conveys the obvious deep interest and delight the author brings to the subject. There are an impressive number of references to substantiate this scholarly text. One minor point that might (subjectively make the book even better would be to place Chapter 14 (Electronic Effects of Silyl Group earlier since it so germane to all of the book. The price is high, but not unreasonably so, and the book can quite rightly claim to be the "Eaborn" of the 2000s.

	Foreword	xxi
	Preface	xxiii
Part I	Fundamentals of Silicon Reactivity: Reactive Intermediates and Reaction Mechanisms	1
1.	Organosilanes: Where to Find Them, What to Call Them, How to Detect Them	3
1.1.	Introduction	3
1.2.	References	5
1.3.	Nomenclature	9
1.4.	NMR Characterization of Silicon-Containing Species	13
1.5.	References	23
2.	Atomic and Molecular Properties of Silicon	27
2.1.	Atomic Properties	27
2.2.	Orbital Interactions of Silicon: Atomic Orbitals	29
2.3.	Molecular Properties of Silicon	31
2.4.	References	36
3.	Silicon-Based Reactive Intermediates	39
3.1.	Silylenes (R[subscript 2]Si:)	40
3.2.	Silylium Ions (R[subscript 3]Si[superscript +])	48
3.3.	Silyl Radicals (R[subscript 3]Si[superscript .])	52
3.4.	Silyl Anions (R[subscript 3]Si[superscript -])	55
3.5.	[pi] Bonds to Silicon	61
3.6.	References	79
4.	Extracoordination at Silicon	97
4.1.	Extracoordination: Silicon as a Lewis Acid	97
4.2.	More Complex Pentacoordinate Compounds	99
4.3.	Reactivity of Extracoordinate Species: Electronic Distribution	101
4.4.	Reactions of Pentacoordinate Systems	103
4.5.	Hexacoordinate Compounds	106
4.6.	Higher Extra Coordinate Species	110
4.7.	References	111
5.	Reaction Mechanisms for Nucleophilic Substitution at Silicon	115
5.1.	Reaction Mechanisms in Carbon Chemistry	115
5.2.	The Study of Stereochemistry, Mechanism, and Silicon: Enantiopure Silanes	116
5.3.	The Role of Extracoordinate Silicon in Nucleophilic Substitution	121
5.4.	Silicon as an Inorganic Element (Rather Than as a Carbon Analogue): Understanding the Stereochemical Outcome	122
5.5.	The Mechanism of Substitution in the Presence of Silaphilic Catalysts	133
5.6.	References	137
Part II	The Formation and Cleavage of Non-Carbon Bonds to Silicon: Applications in Organic and Polymer Chemistry	143
6.	Silicon and Transition Metal Chemistry	145
6.1.	Metal Complexes without Si-Metal Bonds	145
6.2.	[eta superscript 1]-Si-Metal Complexes	150
6.3.	Some Reactions of [eta superscript 1]-Si-Metal Complexes	153
6.4.	Transition Metal Complexes of Stable Silyl Species	155
6.5.	Stabilization of Silicon-Based Reactive Intermediates	156
6.6.	References	163
7.	Hydrosilanes as Reducing Agents	171
7.1.	Si-H Bond Strengths	171
7.2.	Reduction of Organic Functional Groups	172
7.3.	Reduction of Carbocations	175
7.4.	Formation of SiO Bonds Using Hydrosilanes	175
7.5.	References	185
8.	Replacing H with Si: Silicon-Based Reagents	189
8.1.	Trimethylsilyl-Based Reagents	190
8.2.	Silyl Protecting Groups	198
8.3.	Silicon-Tethered Reactions: A Temporary Connection	209
8.4.	Silicon-Protected Nucleophiles I: Silyl Nitronates	215
8.5.	Silicon-Protected Nucleophiles II: Silyl Enol Ethers (Alkenoxysilanes, Enolsilanes)	215
8.6.	References	239
9.	Silicones	256
9.1.	Uses of Silicones	257
9.2.	General Routes to Silicone Cyclics and Oligomers	258
9.3.	Preparing/Modifying High-Molecular-Weight Silicones	261
9.4.	Crosslinking of Silicones	282
9.5.	Silicone-Organic Copolymers	292
9.6.	Degradative Reactions of Silicones	294
9.7.	References	298
10.	Siloxanes Based on T and Q Units	309
10.1.	Silica (Q Units)	309
10.2.	Crystalline and Amorphous Silica	309
10.3.	Ormosils: Organic Modified Sol-Gels	320
10.4.	Silsesquioxanes (RSiO[subscript 3/2]: T Units)	321
10.5.	References	331
11.	Other Silicon-Containing Polymers	340
11.1.	Organic Polymers with Pendant Silyl Groups	340
11.2.	Disilanes	343
11.3.	Polysilanes	347
11.4.	Carbosilane Polymers	355
11.5.	Nitrogen-Containing Silicon Polymers: The Polysilazanes	365
11.6.	Silicon Carbide	366
11.7.	The Preparation of Silicon	367
11.8.	References	367
Part III	The Formation and Cleavage of Silicon-Carbon Bonds: Applications in Organic Synthesis	379
12.	Formation of Si-C Bonds: The Synthesis of Functional Organosilanes	381
12.1.	The Direct Process	382
12.2.	Grignard-Type Reactions	385
12.3.	Other Ways of Generating Carbanions	388
12.4.	Silyl Anions	394
12.5.	Acylsilanes	395
12.6.	Transition Metal-Catalyzed Reactions	397
12.7.	Addition of Cyanotrimethylsilane to Alkynes	400
12.8.	Hydrosilylation	401
12.9.	Formation of Si-C bonds - Some Unusual Approaches	422
12.10.	Functional Organosilanes Prepared from Organosilanes	422
12.11.	Functional Silanes by Oxidation	440
12.12.	References	442
13.	Silicon in a Biological Environment	459
13.1.	Inorganic Silicon Compounds: Silica	459
13.2.	Organic Silicon Compounds	462
13.3.	References	473
14.	Silicon in the Organic World: Electronic Effects of Silyl Groups	480
14.1.	Magnitude of Electronic Effects	480
14.2.	Stabilization of Carbenes, Ions, and Radicals	483
14.3.	References	503
15.	Rearrangements	511
15.1.	Anionic Rearrangements	511
15.2.	Cationic Rearrangements	520
15.3.	Epoxysilanes: Rearrangements and Other Reactions	524
15.4.	Radical Rearrangements	526
15.5.	Carbene Rearrangements	528
15.6.	Concurrent Rearrangements	530
15.7.	Acylsilanes--Silyl Functional Groups That Participate Extensively in Rearrangement Reactions	539
15.8.	References	543
16.	Cleavage of Si-C Bonds	552
16.1.	Temporary Steric Control by Silyl Groups: Now You See It, Now You Don't	552
16.2.	Oxidative Cleavage of Silyl Groups (C-Si[right arrow]C-OH)	558
16.3.	Nucleophile-Induced Desilylation (C-Si[right arrow]C-C)	561
16.4.	Electrophilic-Induced Desilylation (C-Si[right arrow]C-H, C-X, C-C)	569
16.5.	References	596
	Indices of Functional Group Transformations	608
	Subject Index	644