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
Innehållsförteckning
Preface.
Abbreviations.
1. Heavy Analogs of Carbenium Ions: Si-, Ge-, Sn- and
Pb-Centered Cations.
1.1 Introduction.
1.2 Synthesis of RR’R’E¯+Cations (E = Si-Pb).
1.3 Reactions and Synthetic Applications of RRRE¯+
Cations¯16.
1.4 Theoretical Studies.
1.5 Early Studies of RR’R’E¯+ Cations: Free or
Coordinated?
1.6 Stable RR’R’E¯+ Cations.
1.7 Summary and Outlook.
1.8 References.
2. Heavy Analogs of Organic Free Radicals: Si-, Ge-, Sn- and
Pb-Centered Radicals.
2.1 Introduction.
2.2 Early Studies: Transient Species RR’R’E.
2.3 Persistent Radicals (Generation and Identification).
2.4 Stable Radicals.
2.5 Summary and Outlook.
2.6 References.
3. Heavy Analogs of Carbanions: Si-, Ge-, Sn- and Pb-Centered
Anions.
3.1 Introduction.
3.2 Synthesis.
3.3 Structure.
3.4 Reactions and Synthetic Applications.
3.5 Recent Developments.
3.6 Summary and Outlook.
3.7 References.
4. Heavy Analogs of Carbenes: Silylenes, Germylenes,
Stannylenes and Plumbylenes.
4.1 Introduction.
4.2 Generation.
4.3 Spectroscopic Identification.
4.4 Structure.
4.5 Reactions of Transient Species.
4.6 Stable/Persistent Silylenes, Germylenes, Stannylenes and
Plumbylenes.
4.7 Summary and Outlook.
4.8 References.
5. Heavy Analogs of Alkenes, 1, 3-Dienes, Allenes and Alkynes:
Multiply Bonded Derivatives of Si, Ge, Sn and Pb.
5.1 Introduction.
5.2 Early Studies: Generation and Identification.
5.3 Stable Derivatives (Synthesis and Structure).
5.4 Summary and Outlook.
5.5 References.
6. Heavy Analogs of Aromatic Compounds.
6.1 Introduction.
6.2 Early Studies.
6.3 Stable Compounds (Synthesis and Structure).
6.4 Summary and Outlook.
6.5 References.
Index.
Om författaren
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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