Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb: From Phantom Species to Stable Compounds / Edition 1

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Overview

Until recently the low-coordinate compounds of the heavier elements of group 14 were known only as transient, unstable species which were difficult to isolate. However recent developments have led to the stabilisation of these compounds and today heavier group 14 element cations, radicals, anions, carbene analogues, alkene and alkyne analogues and aromatics have all been prepared as highly reactive, stable, fully characterizable and readily available organometallic reagents.

Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb describes the chemistry of this exciting new class of organometallics, with an emphasis on their major similarities and differences with the analogous species in organic chemistry. Topics covered include include the synthesis, structure, reactions and synthetic applications of :

  • Si-, Ge-, Sn and Pb-centered cations, radicals and anions
  • heavy analogues of carbenes: silylenes, germylenes, stannylenes and plumbylenes
  • heavy analogues of alkenes: disilenes, digermenes, distannenes, diplumbenes
  • heavy analogues of alkynes: disilynes, digermynes, distannynes, diplumbynes, and their valence isomers
  • heteronuclear derivatives: silenes, germenes, stannenes, silagermenes, silastannenes, germastannenes
  • heavy analogues of alkenes of the type: >E14=E13-, >E14=E15-, >E14=E16 [where E13, E14, E15 and E16 are elements of the groups 13, 14, 15 and 16]
  • cyclic compounds (three-, four-, five-, and six-membered rings)
  • heavy analogues of 1,3-dienes, allenes and other cumulenes
  • heavy analogues of aromatic compounds; including a comparison between organometallic and organic aromaticity

Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb is an essential guide to this emerging class of organometallic reagents for researchers and students in main group, organometallic, synthetic and silicon chemistry

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Product Details

  • ISBN-13: 9780470725436
  • Publisher: Wiley
  • Publication date: 9/21/2010
  • Edition number: 1
  • Pages: 448
  • Product dimensions: 6.80 (w) x 9.80 (h) x 1.20 (d)

Meet the Author

Vladimir Ya. Lee
Assistant Professor, Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Japan
Vladimir Ya. Lee has worked at the Korea Institute of Science and Technology (Korea), at the Université Paul Sabatier (France), and, since 1998, at the University of Tsukuba (Japan). His research interests lie in the field of highly reactive species: carbene analogues, cations, free radicals, anions, multiply bonded compounds and small rings.

Akira Sekiguchi
Professor, Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Japan
Akira Sekiguchi is Professor of Organic Chemistry at the University of Tsukuba. He received the Japan IBM Science Award in 1996, the Divisional Award of the Chemical Society of Japan (Organic Chemistry) in 1997, and the Alexander von Humboldt Research Award in 2004. His research interests are organosilicon and organolithium chemistry, organogermanium chemistry, and reactive intermediates. In 2006 he received the Kipping Award, the most important prize in the field of silicon chemistry.

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Table of Contents

Preface

Abbreviations

1 Heavy Analogs of Carbenium Ions: Si-, Ge-, Sn- and Pb-Centered Cations 1

1.1 Introduction 1

1.2 Synthesis of RR'R"E+ Cations (E = Si-Pb) 3

1.2.1 From Halides RR'R"EX 3

1.2.2 From Hydrides RR'R"EH 3

1.2.3 From RR'R"E-R" and RR'R"E-ERR'R" 3

1.2.4 From Heavy Carbene Analogs RR'E 5

1.2.5 From Free Radicals RR'R"E 5

1.3 Reactions and Synthetic Applications of RR'R"E+ Cations16 6

1.4 Theoretical Studies 7

1.4.1 Structure of Cations 8

1.4.2 Stability of Cations 8

1.4.3 Calculation of the NMR Chemical Shift of Cations 9

1.4.3.1 29Si NMR Chemical Shift Calculations 10

1.4.3.2 119Sn NMR Chemical Shift Calculations 11

1.5 Early Studies of RR'R"E+ Cations: Free or Coordinated? 11

1.6 Stable RR'R"E+ Cations 16

1.6.1 Intramolecularly Stabilized (Coordinated) Cations 16

1.6.2 Free (Noncoordinated) Cations 29

1.6.2.1 Cyclic π-Conjugated Cations 29

1.6.2.2 Acyclic Cations Lacking π-Conjugation 90 30

1.7 Summary and Outlook 35

1.8 References 36

2 Heavy Analogs of Organic Free Radicals: Si-, Ge-, Sn-and Pb-Centered Radicals 45

2.1 Introduction 45

2.2 Early Studies: Transient Species RR'R"E 47

2.2.1 Generation 47

2.2.2 Structure (Identification) 48

2.2.2.1 Electronic Spectroscopy 48

2.2.2.2 EPR and CIDNP Spectroscopy 49

2.2.2.2.1 EPR Spectroscopy 49

2.2.2.3 Theoretical Calculations 51

2.2.3 Synthetic Applications 52

2.3 Persistent Radicals (Generation and Identification) 53

2.4 Stable Radicals 57

2.4.1 Neutral Radicals 58

2.4.1.1 Cyclic Radicals 58

2.4.1.2 Acyclic Tricoordinate Radicals 60

2.4.2 Charged Radicals 66

2.4.2.1 Anion-radicals 67

2.4.2.1.1 Cyclic Anion-radicals 67

2.4.2.1.2 Acyclic Anion-radicals 68

2.4.2.1.2.1 Heavy Carbenes Anion-radicals 68

2.4.2.1.2.2 Heavy Alkenes Anion-radicals 72

2.4.2.1.2.3 Heavy Alkynes Anion-radicals 74

2.4.2.2 Cation-radicals 77

2.4.3 Stable Biradicals of the Heavy Group 14 Elements 78

2.5 Summary and Outlook 81

2.6 References 82

3 Heavy Analogs of Carbanions: Si-, Ge-, Sn-and Pb-Centered Anions 89

3.1 Introduction 89

3.2 Synthesis 91

3.2.1 Alkyl-substituted Silyl Anions 91

3.2.2 Aryl-substituted Silyl Anions 91

3.2.3 Silyl-substituted Silyl Anions 92

3.2.4 Silyl Anions with Functional Groups 92

3.2.4.1 (Hydrido)Silyllithium Derivatives 92

3.2.4.2 (Halo)Silyllithium Derivatives 93

3.2.4.3 (Amino)Silyllithium Derivatives 93

3.2.4.4 (Alkoxy)Silyllithium Derivatives 94

3.2.4.5 (Acyl)Silyllithium Derivatives (Lithium Sila-enolates) 94

3.2.5 Cyclic Anions 94

3.2.5.1 Silole, Germole and Stannole Anions and Dianions 94

3.2.5.2 Cyclic Oligosilyl Anions 95

3.2.6 Polylithiosilanes 95

3.2.6.1 Tetralithiosilane 95

3.2.6.2 1, 1-Dilithiosilane Derivatives 96

3.2.6.3 1, 2-Dilithiodisilane Derivatives 96

3.2.6.4 1, 3-Dilithiotrisilane and 1, 4-Dilithiotetrasilane Derivatives 97

3.3.7 Germyl, Stannl and Plumbyl Anions 97

3.3 Structure 98

3.3.1 NMR Spectroscopy (Condensed Phase Structure) 98

3.3.2 X-ray Crystallography (Crystal Structure) 101

3.4 Reactions and Synthetic Applications 104

3.5 Recent Developments 109

3.5.1 sp3 Anions 110

3.5.2 sp2 Anions 120

3.5.3 Cyclic and Polycyclic Anions 123

3.6 Summary and Outlook 129

3.7 References 131

4 Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes 139

4.1 Introduction 139

4.2 Generation 140

4.2.1 Photolysis of Acyclic Oligo-and Polymetallanes 140

4.2.2 Photolysis of Cyclic Metallanes 143

4.2.3 Thermolysis of Oligo-and Monometallanes 146

4.2.4 α-Elimination of Silylenoids 148

4.2.5 Heavy Alkene-Heavy Carbene Rearrangements 149

4.3 Spectroscopic Identification 150

4.4 Structure 152

4.4.1 Multiplicity: Singlet vs Triplet 152

4.4.2 Substituent Effects 153

4.5 Reactions of Transient Species 155

4.5.1 Insertion into Single Bonds 156

4.5.2 Addition to Multiple Bonds 159

4.5.2.1 Addition to Alkenes 159

4.5.2.2 Addition to Alkynes 161

4.5.2.3 Addition to 1, 3-Dienes 163

4.5.3 Disilenes/Silenes from Silylenes: Dimerization, Rearrangement 164

4.5.4 Complexation to Transition Metals 166

4.6 Stable/Persistent Silylenes, Germylenes, Stannylenes and Plumbylenes 172

4.6.1 Singlet Species 172

4.6.1.1 Silylenes 173

4.6.1.2 Germylenes 175

4.6.1.3 Stannylenes 179

4.6.1.4 Plumbylenes 182

4.6.2 Triplet Species: Generation and Identification 184

4.7 Summary and Outlook 187

4.8 References 188

5 Heavy Analogs of Alkenes, 1, 3-Dienes, Allenes and Alkynes: Multiply Bonded Derivatives of Si, Ge, Sn and Pb 199

5.1 Introduction 199

5.2 Early Studies: Generation and Identification 200

5.3 Stable Derivatives (Synthesis and Structure) 201

5.3.1 Heavy Analogs of Alkenes (including cyclic compounds) 201

5.3.1.1 Homonuclear Compounds 201

5.3.1.1.1 Disilenes >Si=Si<3c-e, 12 206

5.3.1.1.2 Digermenes>Ge=Ge<5c, 71 225

5.3.1.1.3 Distannenes>Sn=Sn<5c, 71b, d 237

5.3.1.1.4 Diplumbenes>Pb=Pb<5c, 71d 243

5.3.1.2 Heteonuclear Compounds 246

5.3.1.2.1 Group 14/Group 14 Combinations: >E14 = E14'< (E14, E14' = C, Si, Ge, Sn, Pb) 246

5.3.1.2.1.1 Silenes>Si=C<124 246

5.3.1.2.1.2 Germenes >Ge=C<71a, c, 124f, i 256

5.3.1.2.1.3 Stannenes >Sn=C<71b, 124f, i 262

5.3.1.2.1.4 Plumbenes >Pb=C<5a 265

5.3.1.2.1.5 Silagermenes >Si=Ge<124i 265

5.3.1.2.1.6 Silastannes >Si=Sn<124i 268

5.3.1.2.1.7 Germastannenes >Ge=Sn<124i 270

5.3.1.2.2 Group 14/Group 13 Combinations: >E14 = E13- (E14 = Si, Ge; E13 = B, Ga, In) 273

5.3.1.2.3 Group 14/Group 15 Combinations: <E14 = E15- (E14 = Si, Ge, Sn; E15 = N, P, As) 276

5.3.1.2.3.1 Silaimines >Si=N-179 276

5.3.1.2.3.2 Germaimines >Ge=N-71a, c, 191a, b 279

5.3.1.2.3.3 Stannaimines >Sn=N-71b, 191a 281

5.3.1.2.3.4 Phosphasilenes >Si=P-203 282

5.3.1.2.3.5 Phosphagermenes >Ge=P-71a-c, 191a 287

5.3.1.2.3.6 Phosphastannenes >Sn=P-71b, 191a 288

5.3.1.2.3.7 Arsasilenes >Si=As-217 289

5.3.1.2.4 Group 14/Group 16 Combinations >E14 = E16 (E14 = Si, Ge, Sn; E16 = O, S, Se, Te) 290

5.3.1.2.4.1 >E14=O Combinations 290

5.3.1.2.4.2 >E14=S Combinations 293

5.3.1.2.4.3 >E14=Se Combinations 294

5.3.1.2.4.4 >E14=Te Combinations 295

5.3.2 Heavy Analogs of 1, 3-Dienes and Allenes 295

5.3.2.1 Heavy Analogs of 1, 3-Dienes 237 295

5.3.2.2 Heavy Analogs of Allenes245 300

5.3.3 Heavy Analogs of Alkynes: Disilynes, Digermynes, Distannynes, Diplumbynes, and their Valence Isomers260 309

5.3.3.1 Disilynes RSiSiR 310

5.3.3.2 Digermynes RGeGeR (and their Valence Isomers) 313

5.3.3.3 Valence Isomers of Distannynes RSnSnR 314

5.3.3.4 Valence Isomers of Diplumbynes RpbPbR 315

5.3.3.5 Heavy Analogs of Alkynes: Structure and Bonding 315

5.4 Summary and Outlook 319

5.5 References 319

6 Heavy Analogs of Aromatic Compounds 335

6.1 Introduction 335

6.2 Early Studies 338

6.2.1 Transient Species: Generation, Identification and Trapping 338

6.3 Stable Compounds (Synthesis and Structure) 339

6.3.1 2π-Electron Species 339

6.3.1.1 Cyclopropenylium Ion Derivatives 340

6.3.1.2 Cyclobutadiene Dication Derivatives 343

6.3.2 6π-Electron Species 344

6.3.2.1 Benzene (and its Homologs) Derivatives 344

6.3.2.1.1 Theoretical Studies 344

6.3.2.1.2 Experimental Accomplishments 346

6.3.2.2 Cyclopentadienide Ion Derivatives 352

6.3.2.3 Cyclobutadiene Dianion Derivatives 363

6.3.2.4 Cycloheptatrienylium (Tropylium) Ion Derivatives 369

6.3.3 Homoaromaticity 370

6.3.4 Antiaromaticity 375

6.3.4.1 Cyclobutadiene Derivatives 377

6.3.4.2 Cyclopropenyl Anion Derivatives 383

6.3.4.3 Cyclopentadienylium Ion Derivatives 384

6.3.5 Reactivity of Heavy Aromatics: Complexation to Transition Metals 387

6.4 Summary and Outlook 402

6.5 References 403

Index 415

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