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E-raamat: Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb - From Phantom Species to Stable Compounds: From Phantom Species to Stable Compounds [Wiley Online]

(University of Tsukuba, Japan), (University of Tsukuba, Japan)
  • Formaat: 448 pages
  • Ilmumisaeg: 23-Jul-2010
  • Kirjastus: John Wiley & Sons Inc
  • ISBN-10: 470669268
  • ISBN-13: 9780470669266
Teised raamatud teemal:
  • Wiley Online
  • Hind: 231,55 €*
  • * hind, mis tagab piiramatu üheaegsete kasutajate arvuga ligipääsu piiramatuks ajaks
Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb - From Phantom Species to Stable Compounds: From Phantom Species to Stable CompoundsSuurem pilt
  • Formaat: 448 pages
  • Ilmumisaeg: 23-Jul-2010
  • Kirjastus: John Wiley & Sons Inc
  • ISBN-10: 470669268
  • ISBN-13: 9780470669266
Teised raamatud teemal:
Wiley Online e-raamatudRohkem infot Wiley Online kohta
Raamatu kodulehekülg: https://onlinelibrary.wiley.com/doi/book/10.1002/9780470669266
Until recently the low-coordinate compounds of the heavy elements of group 14 were known only as transient, unstable species which were difficult to isolate. However recent developments have led to the stabilization of these compounds and today many have been prepared as stable, highly reactive, fully characterizable and readily available organometallic reagents.

Organometallic Compounds of Low-Coordinate Si, Ge, Sn and Pb describes the synthesis, structure, reactions and synthetic applications of heavy group 14 element cations, radicals, anions, carbene analogues, alkene, diene and alkyne analogues, and aromatics. An emphasis is placed on their major similarities and differences with the analogous species in organic chemistry.

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.



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

Preface xi
Abbreviations xiii
1 Heavy Analogs of Carbenium Ions: Si-, Ge-, Sn- and Pb-Centered Cations
1(44)
1.1 Introduction
1(2)
1.2 Synthesis of RR'R"E+ Cations (E = Si-Pb)
3(3)
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 of RR'R"E+ Cations16
6(1)
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 Shift of Cations
9(1)
1.4.3.1 29Si NMR Chemical Shift Calculations
10(1)
1.4.3.2 119Sn NMR Chemical Shift Calculations
11(1)
1.5 Early Studies of RR'R"E+ Cations: Free or Coordinated?
11(5)
1.6 Stable RR'R"E+ Cations
16(19)
1.6.1 Intramolecularly Stabilized (Coordinated) Cations
16(13)
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 π-Conjugation 90
30(5)
1.7 Summary and Outlook
35(1)
1.8 References
36(9)
2 Heavy Analogs of Organic Free Radicals: Si-, Ge-, Sn-and Pb-Centered Radicals
45(44)
2.1 Introduction
45(2)
2.2 Early Studies: Transient Species RR'R"E
47(6)
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 Identification)
53(4)
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 Anion-radicals
68(4)
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 Group 14 Elements
78(3)
2.5 Summary and Outlook
81(1)
2.6 References
82(7)
3 Heavy Analogs of Carbanions: Si-, Ge-, Sn-and Pb-Centered Anions
89(50)
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 Groups
92(1)
3.2.4.1 (Hydrido)Silyllithium Derivatives
92(1)
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 (Lithium Sila-enolates)
94(1)
3.2.5 Cyclic Anions
94(1)
3.2.5.1 Silole, Germole and Stannole Anions and Dianions
94(1)
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 Derivatives
96(1)
3.2.6.4 1, 3-Dilithiotrisilane and 1, 4-Dilithiotetrasilane Derivatives
97(1)
3.3.7 Germyl, Stannl and Plumbyl Anions
97(1)
3.3 Structure
98(6)
3.3.1 NMR Spectroscopy (Condensed Phase Structure)
98(3)
3.3.2 X-ray Crystallography (Crystal Structure)
101(3)
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, Germylenes, Stannylenes and Plumbylenes
139(60)
4.1 Introduction
139(1)
4.2 Generation
140(10)
4.2.1 Photolysis of Acyclic Oligo-and Polymetallanes
140(3)
4.2.2 Photolysis of Cyclic Metallanes
143(3)
4.2.3 Thermolysis of Oligo-and Monometallanes
146(2)
4.2.4 α-Elimination of Silylenoids
148(1)
4.2.5 Heavy Alkene-Heavy Carbene Rearrangements
149(1)
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: Dimerization, Rearrangement
164(2)
4.5.4 Complexation to Transition Metals
166(6)
4.6 Stable/Persistent Silylenes, Germylenes, Stannylenes and Plumbylenes
172(15)
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 Identification
184(3)
4.7 Summary and Outlook
187(1)
4.8 References
188(11)
5 Heavy Analogs of Alkenes, 1, 3-Dienes, Allenes and Alkynes: Multiply Bonded Derivatives of Si, Ge, Sn and Pb
199(136)
5.1 Introduction
199(1)
5.2 Early Studies: Generation and Identification
200(1)
5.3 Stable Derivatives (Synthesis and Structure)
201(118)
5.3.1 Heavy Analogs of Alkenes (including cyclic compounds)
201(1)
5.3.1.1 Homonuclear Compounds
201(5)
5.3.1.1.1 Disilenes >Si=Si<3c-e, 12
206(19)
5.3.1.1.2 Digermenes>Ge=Ge<5c, 71
225(12)
5.3.1.1.3 Distannenes>Sn=Sn<5c, 71b, d
237(6)
5.3.1.1.4 Diplumbenes>Pb=Pb<5c, 71d
243(3)
5.3.1.2 Heteonuclear Compounds
246(1)
5.3.1.2.1 Group 14/Group 14 Combinations: >E14 = E14'< (E14, E14' = C, Si, Ge, Sn, Pb)
246(1)
5.3.1.2.1.1 Silenes>Si=C<124
246(10)
5.3.1.2.1.2 Germenes >Ge=C<71a, c, 124f, i
256(6)
5.3.1.2.1.3 Stannenes >Sn=C<71b, 124f, i
262(3)
5.3.1.2.1.4 Plumbenes >Pb=C<5a
265(1)
5.3.1.2.1.5 Silagermenes >Si=Ge<124i
265(3)
5.3.1.2.1.6 Silastannes >Si=Sn<124i
268(2)
5.3.1.2.1.7 Germastannenes >Ge=Sn<124i
270(3)
5.3.1.2.2 Group 14/Group 13 Combinations: >E14 = E13- (E14 = Si, Ge; E13 = B, Ga, In)
273(3)
5.3.1.2.3 Group 14/Group 15 Combinations: <E14 = E15- (E14 = Si, Ge, Sn; E15 = N, P, As)
276(1)
5.3.1.2.3.1 Silaimines >Si=N-179
276(3)
5.3.1.2.3.2 Germaimines >Ge=N-71a, c, 191a, b
279(2)
5.3.1.2.3.3 Stannaimines >Sn=N-71b, 191a
281(1)
5.3.1.2.3.4 Phosphasilenes >Si=P-203
282(5)
5.3.1.2.3.5 Phosphagermenes >Ge=P-71a-c, 191a
287(1)
5.3.1.2.3.6 Phosphastannenes >Sn=P-71b, 191a
288(1)
5.3.1.2.3.7 Arsasilenes >Si=As-217
289(1)
5.3.1.2.4 Group 14/Group 16 Combinations >E14 = E16 (E14 = Si, Ge, Sn; E16 = O, S, Se, Te)
290(1)
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 Allenes
295(1)
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: Disilynes, Digermynes, Distannynes, Diplumbynes, and their Valence Isomers260
309(1)
5.3.3.1 Disilynes RSiSiR
310(3)
5.3.3.2 Digermynes RGeGeR (and their Valence Isomers)
313(1)
5.3.3.3 Valence Isomers of Distannynes RSnSnR
314(1)
5.3.3.4 Valence Isomers of Diplumbynes RpbPbR
315(1)
5.3.3.5 Heavy Analogs of Alkynes: Structure and Bonding
315(4)
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, Identification and Trapping
338(1)
6.3 Stable Compounds (Synthesis and Structure)
339(63)
6.3.1 2π-Electron Species
339(1)
6.3.1.1 Cyclopropenylium Ion Derivatives
340(3)
6.3.1.2 Cyclobutadiene Dication Derivatives
343(1)
6.3.2 6π-Electron Species
344(1)
6.3.2.1 Benzene (and its Homologs) Derivatives
344(1)
6.3.2.1.1 Theoretical Studies
344(2)
6.3.2.1.2 Experimental Accomplishments
346(6)
6.3.2.2 Cyclopentadienide Ion Derivatives
352(11)
6.3.2.3 Cyclobutadiene Dianion Derivatives
363(6)
6.3.2.4 Cycloheptatrienylium (Tropylium) Ion Derivatives
369(1)
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 Derivatives
384(3)
6.3.5 Reactivity of Heavy Aromatics: Complexation to Transition Metals
387(15)
6.4 Summary and Outlook
402(1)
6.5 References
403(12)
Index 415
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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