Organo Main Group Chemistry

273 Pages·2011·3.369 MB·English

by  Kin?Ya Akiba(auth.)

ORGANO MAIN GROUP
CHEMISTRY
ORGANO MAIN GROUP
CHEMISTRY
KIN-YA AKIBA
AJOHNWILEY&SONS,INC.,PUBLICATION
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LibraryofCongressCataloging-in-PublicationData:
Akiba,Kin-ya,1936–
Organomaingroupchemistry / Kin-yaAkiba.
p.cm.
ISBN978-0-470-45033-8 (pbk.)
1. Organiccompounds. 2. Organiccompounds–Synthesis. 3. Carboncompounds.
4. ChemistryOrganic. I. Title.
QD251.3.A352011
547–dc22
2010050401
PrintedinSingapore
oBookISBN:9781118025918
ePDFISBN:9781118025871
ePubISBN:9781118025888
10987654321
CONTENTS
Preface ix
1 MainGroupElementsandHeteroatoms:Scopeand
Characteristics 1
1.1 Aufbau Principle and Sign of Orbitals / 1
1.2 Electronic Configuration of an Atom: Main Group Elements
and Heteroatoms / 3
1.3 Fundamental Properties of Main Group Elements / 5
1.4 Acidity of Carboxylic Acid and Substituent Effect / 7
1.5 Heteroatom Effect / 10
1.5.1 Stabilization of α-Carbocation by Resonance:
Stereoelectronic Effect / 10
1.5.2 Coordination with Lewis Acids / 15
References / 16
Notes1: Electronegativity 17
Notes2: ImportanceofFormalLogic-I:OxidationNumber
andFormalCharge 19
Notes3: ImportanceofFormalLogic-II:OctetRule,
Eighteen-ElectronRule,Hypervalence 23
v
vi CONTENTS
2 MainGroupElementEffect 25
2.1 What Is Main Group Element Effect? / 25
2.2 Single Bond Energy and π–Bond Energy / 27
2.3 Hypervalent Compound / 31
2.4 Effect of Hypervalent Bond (1): 3c–4e Bond and
Structure / 33
2.5 Effect of Hypervalent Bond (2): Apicophilicity and
Pseudorotation / 41
2.6 Effect of Hypervalent Bond (3): Ligand Coupling Reaction
(LCR) and Edge Inversion / 45
2.7 Effect of σX−C / 46
∗
2.8 Effect of σ / 48
X−C
Notes4: (σ,σ∗)and(π,π∗):HMO(HueckelMolecularOrbital)
andElectrocyclicReaction 57
3 Lithium,Magnesium,andCopperCompounds 63
3.1 Synthesis / 64
3.2 Structure / 66
3.3 Reaction / 68
3.3.1 Deprotonation as Base / 69
3.3.2 Nucleophilic Reaction / 72
3.3.3 Conjugate Addition of Lithium Dimethylcuprate / 76
References / 77
4 BoronandAluminumCompounds 79
4.1 Synthesis / 80
4.2 Structure / 82
4.3 Reaction / 84
References / 88
5 Silicon,Tin,andLeadCompounds 91
5.1 Synthesis / 92
5.2 Reaction / 94
5.3 Organotin and Lead Compounds / 100
References / 104
Notes5: StableCarbeneandItsComplex 105
6 Phosphorus,Antimony,andBismuthCompounds 111
6.1 Phosphorus Compounds / 112
6.2 Synthesis of Organophosphorus Compounds / 113
CONTENTS vii
6.3 Tertiary Phosphine and Its Nucleophilic Reaction / 115
6.4 Arbuzov Reaction / 117
6.5 Perkow Reaction / 118
6.6 Synthesis of Optically Active Phosphines / 119
6.7 Ylide and Wittig Reaction and Related Ones / 123
6.8 Reactions of Phosphonium Salts and Formation of
Phosphoranes / 131
6.9 Freezing BPR and Its Effect / 138
6.10 Antimony and Bismuth Compounds / 143
References / 146
Notes6: DreamsofStaudingerandWittig 149
Notes7: StereochemistryinNucleophilicSubstitution
ofMX -typeCompounds:InversionorRetention 155
4
7 Sulfur,Selenium,andTelluriumCompounds 159
7.1 Sulfur Compounds / 160
7.2 Synthesis of Organosulfur Compounds / 160
7.3 Reactions of Organosulfur Compounds / 166
7.4 Structure and Reaction of Hypervalent Organosulfur
Compounds / 170
7.5 Selenium and Tellurium Compounds / 175
References / 178
Notes8: InversionMechanismofNH andNF :Vertex
3 3
InversionorEdgeInversion 181
8 OrganohalogenCompounds:FluorineandIodine
Compounds 187
8.1 Synthesis of Chlorine and Bromine Compounds / 188
8.2 Fluorine Compounds / 190
8.3 Iodine Compounds / 195
References / 199
9 AtraneandTransannularInteraction:Formationof
HypervalentBond 201
9.1 Introduction / 201
9.2 Silatrane and Atrane / 202
9.3 Transannular Interaction (1) / 208
9.4 Transannular Interaction (2) / 210
References / 211
viii CONTENTS
10 UnsaturatedCompoundsofMainGroupElementsof
ThirdPeriodandHeavier 213
10.1 Introduction / 213
10.2 Unsaturated Bonds of Group 15 Elements of Third Period and
Heavier / 215
10.3 Unsaturated Bonds of Group 14 Elements of Third Period and
Heavier / 219
10.4 Aromatic Compounds of Group 14 Elements / 222
References / 223
11 LigandCouplingReaction 225
11.1 Introduction / 225
11.2 Selectivity of Ligand Coupling Reaction: Theoretical
Investigation / 226
11.3 Ligand Coupling Reaction of Organic Compounds of
Phosphorus, Antimony, and Bismuth / 227
11.4 Ligand Coupling Reaction of Organic Compounds of Sulfur,
Selenium, and Tellurium / 237
11.5 Ligand Coupling Reaction of Organoiodine Compounds / 241
References / 245
Notes9: HexavalentOrganotelluriumCompounds 247
12 HypervalentCarbonCompounds:CanHexavalent
CarbonExist? 251
12.1 Introduction / 251
12.2 Attempts for Pentacoordinate Hypervalent Carbon
Species / 253
12.3 Synthesis of Pentacoordinate Hypervalent Carbon Species
(10-C-5) and Bond Switching at Carbon and Boron / 254
12.4 Attempts to Hexacoordinate Hypervalent Carbon Species
(12-C-6) / 259
References / 262
Notes10: MainGroupElementPorphyrins 265
Index 269
PREFACE
Thefundamentalandessentialelementoforganiccompoundsis,withoutadoubt,
carbon.Thereareexcellenttextbooksonorganicchemistry,suchasthosewritten
byMcMurry,Jones,Jr.,MorrisonandBoyd,andVollhardtandSchore.Theseare
referred in undergraduate courses internationally and are available in almost all
bookstores dealing with science. On the other hand, main group element chem-
istry has been traditionally described in inorganic chemistry textbooks before
transitionmetalchemistry(suchasinCottonandWilkinson,Huheey,Housecroft
and Sharpe, and Schriver, Atkins and Langford).
Heteroatoms,thatis,elementsofgroups15,16,and17bearingunsharedelec-
tron pair (s) and elements of groups 1, 2, and 12–18 in which valence electrons
reside in sp orbitals, are important elements contained in carbon skeletons; they
modify the character of carbon compounds. The chemistry of the sp elements,
namely, main group elements, has beeninvestigated primarily to discover and to
use their unique characteristics, as compared to carbon.
There are books and reviews on the chemistry of each main group element
dealing with detailed and advanced researches. However, there is no concise
book on organic chemistry focusing on the synthesis, structure, and reaction of
main group element compounds.
This book, Organo Main Group Chemistry, consists of 12 chapters and 10
notes. Chapters 1–8 describe the fundamental and basic organic chemistry of
main group elements that are classified according to their groups. These are
appropriate for use as a textbook. Chapters 9–12 note the recent advances in
the related field of hypervalent (higher coordinate) and hypovalent (lower coor-
dinate) compounds of main group elements. The notes supplement the chapters
by explaining basic ideas and also describing recent research in related fields.
ix
x PREFACE
Chapter 1 describes the fundamental properties of main group elements and
explains the difference between a heteroatom and a main group element. Notes
1–3 remind readers of basic ideas of chemistry, emphasizing the importance
of formal logic. Chapter 2 describes precisely the main group element effect in
contrasttotheheteroatomeffect.Also,theeffectofhypervalentbond,whichdoes
notappearinheteroatomsofasecondperiod,isexplainedinconsiderabledetail.
Note 4 is a refresher on Hueckel molecular orbital (HMO) and electrocyclic
reaction.
Chapters 3–8 discuss the synthesis, structure, and reaction of main group
element compounds. Chapter 3 deals with groups 1 and 2, namely, lithium,
magnesium, and copper compounds. Chapter 4 describes boron and aluminum
compounds, and Chapter 5 explains silicon, tin, and lead compounds.
Chapter 6 describes compounds of group 15 elements of phosphorus, anti-
mony, and bismuth. The synthesis of optically active phosphines, reaction of
ylides, formation of phosphoranes, and effect of freezing pseudorotation are
explained using phosphorus as a representative element. These are essentially
common for compounds of groups 14, 15, 16, and 17, and the chemistry has
beendevelopedonphosphorusbeforethatofsulfurbecauseofitsimportance,and
also for stability in handling the compounds. Note 6 mentions historical aspects
of researches on hypervalent compounds, which stemmed from the dreams of
Staudinger and Wittig. Note 7 explains possible mechanisms on nucleophilic
substitution of MX -type compounds.
4
Chapter7describescompoundsofgroup16elementsofsulfur,selenium,and
tellurium.Note8explainsthemechanismanddynamicaspectsofedgeinversion.
Chapter 8 deals with halogen compounds, with emphasis on fluorine and iodine
compounds because organochlorine and bromine compounds are quite common
and are treated well in textbooks for undergraduates.
Chapters 9, 10, and 11 describe recent advances in researches on main group
elements of third period and heavier ones. Chapter 9 deals with the formation of
hypervalent(highercoordinate)bonds,includingsilatraneandatrane.Chapter10
explainsthesynthesisofhypovalent(lowercoordinate)compoundsofgroups14,
15, and also that of aromatic compounds. Chapter 11 illustrates ligand coupling
reaction(LCR)oncompoundsofgroups15,16,andiodine.Note9illustratesthe
synthesis of hexavalent tellurium compounds and that of a cation and an anion
of pentacoordinate tellurium bearing the same kind of ligand.
Chapter12describesthesynthesisofhypervalentcarboncompounds,namely,
pentacoordinatehypervalentcarbonspecies(10-C-5),andattemptstohexacoordi-
nate(hypervalent)carbonspecies(12-C-6),supportedbytheoreticalcalculations.
Note 10 illustrates the synthesis of main group element porphyrins of Sb and P
in which central atoms are hypervalent.
Referencesthroughout this book are based on arbitrary choices by the author,
andnotatallcomprehensive.Particularly,thereferencesinChapters1–8,except
in Chapter 2, contain basic and fundamental references on the fields, accompa-
niedbynewerones,whereappropriate.Mostconsistofreferencesthattheauthor
has read carefully before and found to contain basic experimental results. They
PREFACE xi
wereusedinlecturesforundergraduateandgraduatecoursesinJapaneseuniver-
sities. Chapters 9–12 deal with recent advances in the related fields; therefore,
references are cited to show basic ideas and recent researches. References for
notes were chosen based on the same standpoint as for the chapters. Advanced
series, such as “Comprehensives” of organic synthesis, organometallic, and het-
erocyclic chemistry and the “Patai’s series” on functional groups were not cited
as references.
In Japanese bookstores dealing with sciences, we find a variety of textbooks
originally writteninEnglish that hadbeentranslatedinto Japanese.For instance,
seven textbooks mentioned at the beginning of this preface, except the one by
Housecroft and Sharpe, had been translated and are being used in Japanese uni-
versities.
There are similar books and countless review articles on specialized topics
originally written in Japanese. The Chemical Society of Japan has been editing
theEncyclopediaofExperimentalChemistry (JikkenKagakuKouza).Therecent
fifth edition consists of 30 volumes; it includes all fields of chemical sciences.
However, the articles written in Japanese can neither be referred in original
research papers of international journals, nor in books written in English. It is
a great pity, but it is the reality. This book was originally written in Japanese
andpublished by KodanshaScientific,Inc.,in Tokyounder the title YuukiTenkei
Genso Kagaku (translated into English as Organo Main Group Chemistry) in
2008. I am grateful to Kodansha Scientific, Inc., for allowing me to use all the
equations and schemes in the Japanese edition, without any restriction, to write
the present revised English version.
I am thankful to the international reviewers nominated by John Wiley &
Sons,whoheartilyrecommendedtopublishthisbookinEnglish. Also,Iwishto
acknowledge the patience and support of my family, and the kind cooperation,
skill, and good cheer of the editors at Wiley.
Professor Emeritus of Hiroshima University Kin-ya Akiba
Tokyo,Japan
November2010