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

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

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  • 製本 Hardcover:ハードカバー版/ページ数 431 p.
  • 言語 ENG
  • 商品コード 9780470725436
  • DDC分類 547.0568

Full Description


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

Table of Contents

Preface                                            xi
Abbreviations xiii
1 Heavy Analogs of Carbenium Ions: Si-, 1 (44)
Ge-, Sn- and Pb-Centered Cations
1.1 Introduction 1 (2)
1.2 Synthesis of RR'R"E+ Cations (E = 3 (3)
Si-Pb)
1.2.1 From Halides RR'R"EX 3 (1)
1.2.2 From Hydrides RR'R"EH 3 (1)
1.2.3 From RR'R"E-R" and RR'R"E-ERR'R" 3 (2)
1.2.4 From Heavy Carbene Analogs RR'E 5 (1)
1.2.5 From Free Radicals RR'R"E 5 (1)
1.3 Reactions and Synthetic Applications 6 (1)
of RR'R"E+ Cations16
1.4 Theoretical Studies 7 (4)
1.4.1 Structure of Cations 8 (1)
1.4.2 Stability of Cations 8 (1)
1.4.3 Calculation of the NMR Chemical 9 (1)
Shift of Cations
1.4.3.1 29Si NMR Chemical Shift 10 (1)
Calculations
1.4.3.2 119Sn NMR Chemical Shift 11 (1)
Calculations
1.5 Early Studies of RR'R"E+ Cations: 11 (5)
Free or Coordinated?
1.6 Stable RR'R"E+ Cations 16 (19)
1.6.1 Intramolecularly Stabilized 16 (13)
(Coordinated) Cations
1.6.2 Free (Noncoordinated) Cations 29 (1)
1.6.2.1 Cyclic π-Conjugated Cations 29 (1)
1.6.2.2 Acyclic Cations Lacking 30 (5)
π-Conjugation 90
1.7 Summary and Outlook 35 (1)
1.8 References 36 (9)
2 Heavy Analogs of Organic Free Radicals: 45 (44)
Si-, Ge-, Sn-and Pb-Centered Radicals
2.1 Introduction 45 (2)
2.2 Early Studies: Transient Species 47 (6)
RR'R"E
2.2.1 Generation 47 (1)
2.2.2 Structure (Identification) 48 (1)
2.2.2.1 Electronic Spectroscopy 48 (1)
2.2.2.2 EPR and CIDNP Spectroscopy 49 (1)
2.2.2.2.1 EPR Spectroscopy 49 (2)
2.2.2.3 Theoretical Calculations 51 (1)
2.2.3 Synthetic Applications 52 (1)
2.3 Persistent Radicals (Generation and 53 (4)
Identification)
2.4 Stable Radicals 57 (24)
2.4.1 Neutral Radicals 58 (1)
2.4.1.1 Cyclic Radicals 58 (2)
2.4.1.2 Acyclic Tricoordinate Radicals 60 (6)
2.4.2 Charged Radicals 66 (1)
2.4.2.1 Anion-radicals 67 (1)
2.4.2.1.1 Cyclic Anion-radicals 67 (1)
2.4.2.1.2 Acyclic Anion-radicals 68 (1)
2.4.2.1.2.1 Heavy Carbenes 68 (4)
Anion-radicals
2.4.2.1.2.2 Heavy Alkenes Anion-radicals 72 (2)
2.4.2.1.2.3 Heavy Alkynes Anion-radicals 74 (3)
2.4.2.2 Cation-radicals 77 (1)
2.4.3 Stable Biradicals of the Heavy 78 (3)
Group 14 Elements
2.5 Summary and Outlook 81 (1)
2.6 References 82 (7)
3 Heavy Analogs of Carbanions: Si-, Ge-, 89 (50)
Sn-and Pb-Centered Anions
3.1 Introduction 89 (2)
3.2 Synthesis 91 (7)
3.2.1 Alkyl-substituted Silyl Anions 91 (1)
3.2.2 Aryl-substituted Silyl Anions 91 (1)
3.2.3 Silyl-substituted Silyl Anions 92 (1)
3.2.4 Silyl Anions with Functional 92 (1)
Groups
3.2.4.1 (Hydrido)Silyllithium 92 (1)
Derivatives
3.2.4.2 (Halo)Silyllithium Derivatives 93 (1)
3.2.4.3 (Amino)Silyllithium Derivatives 93 (1)
3.2.4.4 (Alkoxy)Silyllithium Derivatives 94 (1)
3.2.4.5 (Acyl)Silyllithium Derivatives 94 (1)
(Lithium Sila-enolates)
3.2.5 Cyclic Anions 94 (1)
3.2.5.1 Silole, Germole and Stannole 94 (1)
Anions and Dianions
3.2.5.2 Cyclic Oligosilyl Anions 95 (1)
3.2.6 Polylithiosilanes 95 (1)
3.2.6.1 Tetralithiosilane 95 (1)
3.2.6.2 1, 1-Dilithiosilane Derivatives 96 (1)
3.2.6.3 1, 2-Dilithiodisilane 96 (1)
Derivatives
3.2.6.4 1, 3-Dilithiotrisilane and 1, 97 (1)
4-Dilithiotetrasilane Derivatives
3.3.7 Germyl, Stannl and Plumbyl Anions 97 (1)
3.3 Structure 98 (6)
3.3.1 NMR Spectroscopy (Condensed Phase 98 (3)
Structure)
3.3.2 X-ray Crystallography (Crystal 101 (3)
Structure)
3.4 Reactions and Synthetic Applications 104 (5)
3.5 Recent Developments 109 (20)
3.5.1 sp3 Anions 110 (10)
3.5.2 sp2 Anions 120 (3)
3.5.3 Cyclic and Polycyclic Anions 123 (6)
3.6 Summary and Outlook 129 (2)
3.7 References 131 (8)
4 Heavy Analogs of Carbenes: Silylenes, 139 (60)
Germylenes, Stannylenes and Plumbylenes
4.1 Introduction 139 (1)
4.2 Generation 140 (10)
4.2.1 Photolysis of Acyclic Oligo-and 140 (3)
Polymetallanes
4.2.2 Photolysis of Cyclic Metallanes 143 (3)
4.2.3 Thermolysis of Oligo-and 146 (2)
Monometallanes
4.2.4 α-Elimination of Silylenoids 148 (1)
4.2.5 Heavy Alkene-Heavy Carbene 149 (1)
Rearrangements
4.3 Spectroscopic Identification 150 (2)
4.4 Structure 152 (3)
4.4.1 Multiplicity: Singlet vs Triplet 152 (1)
4.4.2 Substituent Effects 153 (2)
4.5 Reactions of Transient Species 155 (17)
4.5.1 Insertion into Single Bonds 156 (3)
4.5.2 Addition to Multiple Bonds 159 (1)
4.5.2.1 Addition to Alkenes 159 (2)
4.5.2.2 Addition to Alkynes 161 (2)
4.5.2.3 Addition to 1, 3-Dienes 163 (1)
4.5.3 Disilenes/Silenes from Silylenes: 164 (2)
Dimerization, Rearrangement
4.5.4 Complexation to Transition Metals 166 (6)
4.6 Stable/Persistent Silylenes, 172 (15)
Germylenes, Stannylenes and Plumbylenes
4.6.1 Singlet Species 172 (1)
4.6.1.1 Silylenes 173 (2)
4.6.1.2 Germylenes 175 (4)
4.6.1.3 Stannylenes 179 (3)
4.6.1.4 Plumbylenes 182 (2)
4.6.2 Triplet Species: Generation and 184 (3)
Identification
4.7 Summary and Outlook 187 (1)
4.8 References 188 (11)
5 Heavy Analogs of Alkenes, 1, 3-Dienes, 199 (136)
Allenes and Alkynes: Multiply Bonded
Derivatives of Si, Ge, Sn and Pb
5.1 Introduction 199 (1)
5.2 Early Studies: Generation and 200 (1)
Identification
5.3 Stable Derivatives (Synthesis and 201 (118)
Structure)
5.3.1 Heavy Analogs of Alkenes 201 (1)
(including cyclic compounds)
5.3.1.1 Homonuclear Compounds 201 (5)
5.3.1.1.1 Disilenes >Si=Si<3c-e, 206 (19)
12
5.3.1.1.2 Digermenes>Ge=Ge<5c, 71 225 (12)
5.3.1.1.3 Distannenes>Sn=Sn<5c, 237 (6)
71b, d
5.3.1.1.4 Diplumbenes>Pb=Pb<5c, 243 (3)
71d
5.3.1.2 Heteonuclear Compounds 246 (1)
5.3.1.2.1 Group 14/Group 14 246 (1)
Combinations: >E14 = E14'< (E14,
E14' = C, Si, Ge, Sn, Pb)
5.3.1.2.1.1 Silenes>Si=C<124 246 (10)
5.3.1.2.1.2 Germenes >Ge=C<71a, 256 (6)
c, 124f, i
5.3.1.2.1.3 Stannenes >Sn=C<71b, 262 (3)
124f, i
5.3.1.2.1.4 Plumbenes >Pb=C<5a 265 (1)
5.3.1.2.1.5 Silagermenes 265 (3)
>Si=Ge<124i
5.3.1.2.1.6 Silastannes 268 (2)
>Si=Sn<124i
5.3.1.2.1.7 Germastannenes 270 (3)
>Ge=Sn<124i
5.3.1.2.2 Group 14/Group 13 273 (3)
Combinations: >E14 = E13- (E14 = Si,
Ge; E13 = B, Ga, In)
5.3.1.2.3 Group 14/Group 15 276 (1)
Combinations: <E14 = E15- (E14 = Si,
Ge, Sn; E15 = N, P, As)
5.3.1.2.3.1 Silaimines >Si=N-179 276 (3)
5.3.1.2.3.2 Germaimines >Ge=N-71a, 279 (2)
c, 191a, b
5.3.1.2.3.3 Stannaimines >Sn=N-71b, 281 (1)
191a
5.3.1.2.3.4 Phosphasilenes >Si=P-203 282 (5)
5.3.1.2.3.5 Phosphagermenes 287 (1)
>Ge=P-71a-c, 191a
5.3.1.2.3.6 Phosphastannenes 288 (1)
>Sn=P-71b, 191a
5.3.1.2.3.7 Arsasilenes >Si=As-217 289 (1)
5.3.1.2.4 Group 14/Group 16 290 (1)
Combinations >E14 = E16 (E14 = Si,
Ge, Sn; E16 = O, S, Se, Te)
5.3.1.2.4.1 >E14=O Combinations 290 (3)
5.3.1.2.4.2 >E14=S Combinations 293 (1)
5.3.1.2.4.3 >E14=Se Combinations 294 (1)
5.3.1.2.4.4 >E14=Te Combinations 295 (1)
5.3.2 Heavy Analogs of 1, 3-Dienes and 295 (1)
Allenes
5.3.2.1 Heavy Analogs of 1, 3-Dienes 237 295 (5)
5.3.2.2 Heavy Analogs of Allenes245 300 (9)
5.3.3 Heavy Analogs of Alkynes: 309 (1)
Disilynes, Digermynes, Distannynes,
Diplumbynes, and their Valence
Isomers260
5.3.3.1 Disilynes RSiSiR 310 (3)
5.3.3.2 Digermynes RGeGeR (and their 313 (1)
Valence Isomers)
5.3.3.3 Valence Isomers of Distannynes 314 (1)
RSnSnR
5.3.3.4 Valence Isomers of Diplumbynes 315 (1)
RpbPbR
5.3.3.5 Heavy Analogs of Alkynes: 315 (4)
Structure and Bonding
5.4 Summary and Outlook 319 (1)
5.5 References 319 (16)
6 Heavy Analogs of Aromatic Compounds 335 (80)
6.1 Introduction 335 (3)
6.2 Early Studies 338 (1)
6.2.1 Transient Species: Generation, 338 (1)
Identification and Trapping
6.3 Stable Compounds (Synthesis and 339 (63)
Structure)
6.3.1 2π-Electron Species 339 (1)
6.3.1.1 Cyclopropenylium Ion Derivatives 340 (3)
6.3.1.2 Cyclobutadiene Dication 343 (1)
Derivatives
6.3.2 6π-Electron Species 344 (1)
6.3.2.1 Benzene (and its Homologs) 344 (1)
Derivatives
6.3.2.1.1 Theoretical Studies 344 (2)
6.3.2.1.2 Experimental Accomplishments 346 (6)
6.3.2.2 Cyclopentadienide Ion 352 (11)
Derivatives
6.3.2.3 Cyclobutadiene Dianion 363 (6)
Derivatives
6.3.2.4 Cycloheptatrienylium 369 (1)
(Tropylium) Ion Derivatives
6.3.3 Homoaromaticity 370 (5)
6.3.4 Antiaromaticity 375 (2)
6.3.4.1 Cyclobutadiene Derivatives 377 (6)
6.3.4.2 Cyclopropenyl Anion Derivatives 383 (1)
6.3.4.3 Cyclopentadienylium Ion 384 (3)
Derivatives
6.3.5 Reactivity of Heavy Aromatics: 387 (15)
Complexation to Transition Metals
6.4 Summary and Outlook 402 (1)
6.5 References 403 (12)
Index 415