TY - BOOK AU - Lee,Vladimir Ya AU - Sekiguchi,Akira TI - Organometallic compounds of low-coordinate Si, Ge, Sn, and Pb: from phantom species to stable compounds SN - 9780470725436 AV - QD411 .L44 2010 PY - 2010/// CY - Chichester, West Sussex, U.K. PB - Wiley KW - Organometallic compounds N1 - Includes bibliographical references and index; Contents; 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) ; 1.2.1 From Halides RR'R"EX ; 1.2.2 From Hydrides RR'R"EH ; 1.2.3 From RR'R"E-R" and RR'R"E-ERR'R" ; 1.2.4 From Heavy Carbene Analogs RR'E ; 1.2.5 From Free Radicals RR'R"E ; 1.3 Reactions and Synthetic Applications of RR'R"E+ Cations16 ; 1.4 Theoretical Studies ; 1.4.1 Structure of Cations ; 1.4.2 Stability of Cations ; 1.4.3 Calculation of the NMR Chemical Shift of Cations ; 1.4.3.1 29Si NMR Chemical Shift Calculations ; 1.4.3.2 119Sn NMR Chemical Shift Calculations ; 1.5 Early Studies of RR'R"E+ Cations: Free or Coordinated? ; 1.6 Stable RR'R"E+ Cations ; 1.6.1 Intramolecularly Stabilized (Coordinated) Cations ; 1.6.2 Free (Noncoordinated) Cations ; 1.6.2.1 Cyclic π-Conjugated Cations ; 1.6.2.2 Acyclic Cations Lacking π-Conjugation 90 ; 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 ; 2.2.1 Generation ; 2.2.2 Structure (Identification) ; 2.2.2.1 Electronic Spectroscopy ; 2.2.2.2 EPR and CIDNP Spectroscopy ; 2.2.2.2.1 EPR Spectroscopy ; 2.2.2.3 Theoretical Calculations ; 2.2.3 Synthetic Applications ; 2.3 Persistent Radicals (Generation and Identification) ; 2.4 Stable Radicals ; 2.4.1 Neutral Radicals ; 2.4.1.1 Cyclic Radicals ; 2.4.1.2 Acyclic Tricoordinate Radicals ; 2.4.2 Charged Radicals ; 2.4.2.1 Anion-radicals ; 2.4.2.1.1 Cyclic Anion-radicals ; 2.4.2.1.2 Acyclic Anion-radicals ; 2.4.2.1.2.1 Heavy Carbenes Anion-radicals ; 2.4.2.1.2.2 Heavy Alkenes Anion-radicals ; 2.4.2.1.2.3 Heavy Alkynes Anion-radicals ; 2.4.2.2 Cation-radicals ; 2.4.3 Stable Biradicals of the Heavy Group 14 Elements ; 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 ; 3.2.1 Alkyl-substituted Silyl Anions ; 3.2.2 Aryl-substituted Silyl Anions ; 3.2.3 Silyl-substituted Silyl Anions ; 3.2.4 Silyl Anions with Functional Groups ; 3.2.4.1 (Hydrido)Silyllithium Derivatives ; 3.2.4.2 (Halo)Silyllithium Derivatives ; 3.2.4.3 (Amino)Silyllithium Derivatives ; 3.2.4.4 (Alkoxy)Silyllithium Derivatives ; 3.2.4.5 (Acyl)Silyllithium Derivatives (Lithium Sila-enolates) ; 3.2.5 Cyclic Anions ; 3.2.5.1 Silole, Germole and Stannole Anions and Dianions ; 3.2.5.2 Cyclic Oligosilyl Anions ; 3.2.6 Polylithiosilanes ; 3.2.6.1 Tetralithiosilane ; 3.2.6.2 1, 1-Dilithiosilane Derivatives ; 3.2.6.3 1, 2-Dilithiodisilane Derivatives ; 3.2.6.4 1, 3-Dilithiotrisilane and 1, 4-Dilithiotetrasilane Derivatives ; 3.3.7 Germyl, Stannl and Plumbyl Anions ; 3.3 Structure ; 3.3.1 NMR Spectroscopy (Condensed Phase Structure) ; 3.3.2 X-ray Crystallography (Crystal Structure) ; 3.4 Reactions and Synthetic Applications ; 3.5 Recent Developments ; 3.5.1 sp3 Anions ; 3.5.2 sp2 Anions ; 3.5.3 Cyclic and Polycyclic Anions ; 3.6 Summary and Outlook ; 3.7 References ; 4 Heavy Analogs of Carbenes: Silylenes, Germylenes, Stannylenes and Plumbylenes ; 4.1 Introduction ; 4.2 Generation ; 4.2.1 Photolysis of Acyclic Oligo-and Polymetallanes ; 4.2.2 Photolysis of Cyclic Metallanes ; 4.2.3 Thermolysis of Oligo-and Monometallanes ; 4.2.4 α-Elimination of Silylenoids ; 4.2.5 Heavy Alkene-Heavy Carbene Rearrangements ; 4.3 Spectroscopic Identification ; 4.4 Structure ; 4.4.1 Multiplicity: Singlet vs Triplet ; 4.4.2 Substituent Effects ; 4.5 Reactions of Transient Species ; 4.5.1 Insertion into Single Bonds ; 4.5.2 Addition to Multiple Bonds ; 4.5.2.1 Addition to Alkenes ; 4.5.2.2 Addition to Alkynes ; 4.5.2.3 Addition to 1, 3-Dienes ; 4.5.3 Disilenes/Silenes from Silylenes: Dimerization, Rearrangement ; 4.5.4 Complexation to Transition Metals ; 4.6 Stable/Persistent Silylenes, Germylenes, Stannylenes and Plumbylenes ; 4.6.1 Singlet Species ; 4.6.1.1 Silylenes ; 4.6.1.2 Germylenes ; 4.6.1.3 Stannylenes ; 4.6.1.4 Plumbylenes ; 4.6.2 Triplet Species: Generation and Identification ; 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) ; 5.3.1 Heavy Analogs of Alkenes (including cyclic compounds) ; 5.3.1.1 Homonuclear Compounds ; 5.3.1.1.1 Disilenes >Si=Si<3c-e, 12 ; 5.3.1.1.2 Digermenes>Ge=Ge<5c, 71 ; 5.3.1.1.3 Distannenes>Sn=Sn<5c, 71b, d ; 5.3.1.1.4 Diplumbenes>Pb=Pb<5c, 71d ; 5.3.1.2 Heteonuclear Compounds ; 5.3.1.2.1 Group 14/Group 14 Combinations: >E14 = E14'< (E14, E14' = C, Si, Ge, Sn, Pb) ; 5.3.1.2.1.1 Silenes>Si=C<124 ; 5.3.1.2.1.2 Germenes >Ge=C<71a, c, 124f, i ; 5.3.1.2.1.3 Stannenes >Sn=C<71b, 124f, i ; 5.3.1.2.1.4 Plumbenes >Pb=C<5a ; 5.3.1.2.1.5 Silagermenes >Si=Ge<124i ; 5.3.1.2.1.6 Silastannes >Si=Sn<124i ; 5.3.1.2.1.7 Germastannenes >Ge=Sn<124i ; 5.3.1.2.2 Group 14/Group 13 Combinations: >E14 = E13- (E14 = Si, Ge; E13 = B, Ga, In) ; 5.3.1.2.3 Group 14/Group 15 Combinations: Si=N-179 ; 5.3.1.2.3.2 Germaimines >Ge=N-71a, c, 191a, b ; 5.3.1.2.3.3 Stannaimines >Sn=N-71b, 191a ; 5.3.1.2.3.4 Phosphasilenes >Si=P-203 ; 5.3.1.2.3.5 Phosphagermenes >Ge=P-71a-c, 191a ; 5.3.1.2.3.6 Phosphastannenes >Sn=P-71b, 191a ; 5.3.1.2.3.7 Arsasilenes >Si=As-217 ; 5.3.1.2.4 Group 14/Group 16 Combinations >E14 = E16 (E14 = Si, Ge, Sn; E16 = O, S, Se, Te) ; 5.3.1.2.4.1 >E14=O Combinations ; 5.3.1.2.4.2 >E14=S Combinations ; 5.3.1.2.4.3 >E14=Se Combinations ; 5.3.1.2.4.4 >E14=Te Combinations ; 5.3.2 Heavy Analogs of 1, 3-Dienes and Allenes ; 5.3.2.1 Heavy Analogs of 1, 3-Dienes 237 ; 5.3.2.2 Heavy Analogs of Allenes245 ; 5.3.3 Heavy Analogs of Alkynes: Disilynes, Digermynes, Distannynes, Diplumbynes, and their Valence Isomers260 ; 5.3.3.1 Disilynes RSiSiR ; 5.3.3.2 Digermynes RGeGeR (and their Valence Isomers) ; 5.3.3.3 Valence Isomers of Distannynes RSnSnR ; 5.3.3.4 Valence Isomers of Diplumbynes RpbPbR ; 5.3.3.5 Heavy Analogs of Alkynes: Structure and Bonding ; 5.4 Summary and Outlook ; 5.5 References ; 6 Heavy Analogs of Aromatic Compounds ; 6.1 Introduction ; 6.2 Early Studies ; 6.2.1 Transient Species: Generation, Identification and Trapping ; 6.3 Stable Compounds (Synthesis and Structure) ; 6.3.1 2π-Electron Species ; 6.3.1.1 Cyclopropenylium Ion Derivatives ; 6.3.1.2 Cyclobutadiene Dication Derivatives ; 6.3.2 6π-Electron Species ; 6.3.2.1 Benzene (and its Homologs) Derivatives ; 6.3.2.1.1 Theoretical Studies ; 6.3.2.1.2 Experimental Accomplishments ; 6.3.2.2 Cyclopentadienide Ion Derivatives ; 6.3.2.3 Cyclobutadiene Dianion Derivatives ; 6.3.2.4 Cycloheptatrienylium (Tropylium) Ion Derivatives ; 6.3.3 Homoaromaticity ; 6.3.4 Antiaromaticity ; 6.3.4.1 Cyclobutadiene Derivatives ; 6.3.4.2 Cyclopropenyl Anion Derivatives ; 6.3.4.3 Cyclopentadienylium Ion Derivatives ; 6.3.5 Reactivity of Heavy Aromatics: Complexation to Transition Metals ; 6.4 Summary and Outlook ; 6.5 References ; Index ER -