Table Of ContentHandbook of Chalcogen Chemistry
New Perspectives in Sulfur, Selenium and Tellurium
2nd Edition, Volume 1
Handbook of Chalcogen
Chemistry
New Perspectives in Sulfur, Selenium and
Tellurium
nd
2 Edition, Volume 1
Edited by
Francesco Antonio Devillanova
Complesso Universitario di Monserrato, Italy
Email: [email protected]
Wolf-Walther du Mont
Technische Universita¨t Braunschweig, Germany
Email: [email protected]
ISBN: 978-1-84973-623-7
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
rTheRoyalSocietyofChemistry2013
Allrightsreserved
Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesorfor
privatestudy,criticismorreview,aspermittedundertheCopyright,DesignsandPatents
Act1988andtheCopyrightandRelatedRightsRegulations2003,thispublicationmaynot
bereproduced,storedortransmitted,inanyformorbyanymeans,withouttheprior
permissioninwritingofTheRoyalSocietyofChemistryorthecopyrightowner,orinthe
caseofreproductioninaccordancewiththetermsoflicencesissuedbytheCopyright
LicensingAgencyintheUK,orinaccordancewiththetermsofthelicencesissuedbythe
appropriateReproductionRightsOrganizationoutsidetheUK.Enquiriesconcerning
reproductionoutsidethetermsstatedhereshouldbesenttoTheRoyalSocietyof
Chemistryattheaddressprintedonthispage.
TheRSCisnotresponsibleforindividualopinionsexpressedinthiswork.
PublishedbyTheRoyalSocietyofChemistry,
ThomasGrahamHouse,SciencePark,MiltonRoad,
CambridgeCB40WF,UK
RegisteredCharityNumber207890
Visitourwebsiteatwww.rsc.org/books
PrintedintheUnitedKingdombyHenryLingLimited,Dorchester,DT11HD,UK
Preface
This second edition of the Handbook of Chalcogen Chemistry appears only six
yearsafterthefirstedition.Theneedtoprepareaneweditionsosoonhastwo
causes:first,someimportanttopicsofthechemistryofchalcogenelementswere
not included in the first edition for various reasons and secondly, chalcogen
chemistry continues to grow rapidly. The graph referred to in Chapter 11.3,
illustrating the remarkable increase of interest in dichalcogenolene chemistry,
shows that the number of papers published in the last decade has been greater
thanthatofallpapersonthesametopicpublishedupto2000.Atthesametime,
thechemistryofseleniumandtelluriumisbecomingincreasinglyimportantwith
respect to that of sulfur in some particular fields such as semiconductors or
nanoparticlesandquantumdotsbased onpolychalcogenides.Inthepreface to
thefirstedition,weindicatedthemainfactorsthathadledtoamarkedincrease
ofinterestinthechemistryofseleniumandtellurium.Here,weconfirmthattwo
mainfactors,closelyconnectedwitheachother,havecontributedfurthertothis
development: (1) the considerable progress in crystallographic techniques and
(2)thegreatvarietyoftechnologicalapplicationsthathavebeenfoundformany
compounds of these elements. As our knowledge of the structural features of
particular aggregates and of their functional mechanisms increases, new
chalcogen compounds are being designed and organized in the solid state to
improve their performance. The continuous demand for new compounds has
stimulated the search for new sophisticated synthetic methodologies, that,
particularly for the selenium and tellurium compounds, utilize the elements in
their elemental state and thus avoid the use of noxious reagents.
Thissecondeditionisorganizedinasimilarwaytothefirst.Maintainingthe
periodictableasaguideline,thechaptersofthefirstparthavebeensubstantially
updatedtotheendof2011.Thesystematicoverviewofchalcogencompoundsin
combinationwiththemaingroupelementsoftheperiodictable,fromboronto
thehalogens,includingthechalcogensthemselves,offersacompleteaccountof
HandbookofChalcogenChemistry:NewPerspectivesinSulfur,SeleniumandTellurium,
2ndEdition,Volume1
EditedbyFrancescoAntonioDevillanovaandWolf-WaltherduMont
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
vi Preface
all the relevant chalcogen compounds. The overview is completed by the two
chapters on metal chalcogenides and polychalcogenides. The second part has
beenextendedwithrespecttothefirsteditionbysomeimportantchaptersinthe
fields of biological chemistry and material chemistry, and by a new chapter on
the theoretical calculations and NMR spectroscopy. All these chapters have
been included not only to improve the balance between the two parts of the
handbook, but also to consider important aspects of the chemistry of the
chalcogenelementsthatareincreasingthescopefortheirpotentialapplications.
We can maintain that, while thefirst part can be considered to contain mainly
aspects of fundamental research, the second part emphasizes the ambitious
purpose of the handbook in pointing out the increasing role of chalcogen
chemistry in satisfying the continuous need for new materials for specific
applicationsinmanyfields.However,theapparentseparationbetweenthetwo
parts is simply one of convenience since they are intimately connected; the
chapters in thesecond part represent further developments of those in thefirst
part. Furthermore, fundamental research often opens up new and unexpected
developments, thus proving once more, if proof were necessary, that the
separation between fundamental and applied research is arbitrary and
irrelevant.Therecentdiscoverythatthering-openingpolymerizationofS N to
2 2
form a conducting material has potential application in forensic science (rapid
imaging of latent fingerprints) represents a surprising development in
chalcogen/nitrogen chemistry and underlines yet again the importance of
fundamental research. Instead of an artificial separation between fundamental
andappliedresearch,wehopetheHandbookclearlydemonstratesthenecessity
of a multidisciplinary approach to tackle any research problem. As a unique
example, we point out that in the explosive development of nanoscience and
nanotechnologyoverthelastfewyears,metalchalcogenidequantumdotshave
proved to be interesting materials in terms of their peculiar optical, magnetic,
electronic, and catalytic properties. Their characteristics as light-emitting
diodes, or as solar cells, or in biomedicine, will stimulate synthetic chemists to
develop new compounds with improved efficiency. Though not exhaustive, the
book includes mainlytheresults fromthelast decade andillustratesthetrends
of the most striking research work. Particular attention has been paid by the
authorstoupdating theliterature ascompletelyaspossible totheendof2011.
Itisour hope thatthe book willserve asareference work foryears tocome.
The multidisciplinary approach, with chapters devoted to biological, materials,
and supramolecular chemistry, renders the book an important source of
informationnotonlyforchemistsbutalsoforphysicists,biochemists,andother
researcherswhodealwithchalcogencompounds.Wehopethebookmayinduce
sufficient curiosity in readers toattract themtowards thisbranchof chemistry.
We are greatly indebted to all the authors for their commitment.
Francesco Antonio Devillanova
Complesso Universitario di Monserrato, Italy
Wolf-Walther du Mont
Technische Universita¨t Braunschweig, Germany
Contents
Introduction 1
F. A. Devillanova and W.-W. duMont
Volume 1
Chapter 1 Compounds Containing Boron–Chalcogen Bonds 5
Michael A. Beckett
1.1 Introduction 5
1.2 Reviews 5
1.3 Polyhedral Boron Hydride Derivatives 6
1.3.1 Species with Exo B–Chalcogen Bonds 6
1.3.2 SpecieswithChalcogenAtomsWithinthe
Polyhedral Cage 10
1.4 Chalcogenoborates 16
1.5 Heterocycles 19
1.6 Miscellaneous 21
Abbreviations 24
References 24
Compounds Containing the Carbon-Chalcogen Bond (E¼S, Se, Te)
Chapter 2.1 Thiolates, Selenolates, and Tellurolates 37
M. Concepcio´n Gimeno
2.1.1 Introduction 37
2.1.2 Synthetic Routes of Ligands and Metal
Chalcogenolates 38
2.1.2.1 Synthesis of the Chalcogenols 38
2.1.2.2 Synthesis of Metal Chalcogenolates 38
HandbookofChalcogenChemistry:NewPerspectivesinSulfur,SeleniumandTellurium,
2ndEdition,Volume1
EditedbyFrancescoAntonioDevillanovaandWolf-WaltherduMont
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
viii Contents
2.1.3 Alkali and Alkaline Earth Derivatives 40
2.1.4 Main Group Metal Derivatives 44
2.1.4.1 Zinc, Cadmium and Mercury 44
2.1.4.2 Aluminium, Gallium, Indium, and
Thallium 46
2.1.4.3 Germanium, Tin, and Lead 47
2.1.4.4 Antimony and Bismuth 48
2.1.5 Transition Metal Derivatives 49
2.1.5.1 Early Transition Metals 49
2.1.5.2 Chromium, Molybdenum, and
Tungsten 50
2.1.5.3 Manganese, Technetium, and Rhenium 52
2.1.5.4 Iron, Ruthenium, and Osmium 54
2.1.5.5 Cobalt, Rhodium, and Iridium 56
2.1.5.6 Nickel, Palladium, and Platinum 58
2.1.5.7 Copper, Silver, and Gold 60
2.1.6 Rare Earth Derivatives 63
2.1.7 Conclusions 65
Acknowledgements 65
References 65
Chapter2.2 Thioamides,Thioureas,andRelatedSeleniumandTellurium
Compounds 94
Mamoru Koketsu
2.2.1 Introduction 94
2.2.2 Thioamides 94
2.2.2.1 Synthesis of Thioamides 95
2.2.2.2 Heterocycles Using Thioamides 96
2.2.2.3 Transformation of Thioamides 100
2.2.2.4 Catalysis 102
2.2.2.5 Biological Activities 102
2.2.3 Thioureas 102
2.2.3.1 Synthesis of Thioureas 102
2.2.3.2 Heterocycles Using Thioureas 103
2.2.3.3 Transformation of Thioureas 105
2.2.3.4 Catalysis 106
2.2.4 Selenoamides and Selenoureas 107
2.2.4.1 Synthesis of Selenoamides and
Selenoureas 107
2.2.4.2 Transformation 108
2.2.4.3 Heterocycles Using Selenoamides and
Selenoureas 108
2.2.5 Telluroamides 111
References 112
Contents ix
Chapter 2.3 Chalcogenone C¼E Compounds (E¼S, Se, Te) 118
Gaetano Verani and Alessandra Garau
2.3.1 Introduction 118
2.3.1.1 Tautomeric Equilibria 121
2.3.1.2 Polymerization and Oligomerization
Reactions 122
2.3.2 Thioketones (Thiones) 123
2.3.2.1 Syntheses 123
2.3.2.2 Reactivity 126
2.3.3 Selenoketones (Selones) 136
2.3.3.1 Syntheses 136
2.3.3.2 Reactivity 140
2.3.4 Telluroketones (Tellones) 146
2.3.4.1 Syntheses 146
2.3.4.2 Reactivity 147
Abbreviations 148
References 149
Chapter 3 Compounds Having Both a Single Bond and a Double Bond
(Heavy Ketones) between Si, Ge, or Sn and Chalcogens
(S, Se, and Te) 160
Nobuhiro Takeda and Norihiro Tokitoh
3.1 Introduction 160
3.2 Compounds Having a Single Bond between
Si, Ge, or Sn and Chalcogens 161
3.2.1 Introduction 161
3.2.2 Synthesis and Properties of 5- and
6-Coordinate Silicon Compounds Bearing
an Si–E (E¼S, Se, Te) Single Bond 161
3.2.3 Compounds Containing [M E ]n(cid:2)
x y
(M¼Ge, Sn; E¼S, Se, Te) Anions 168
3.3 Compounds Having a Double Bond between Si,
Ge, or Sn and Chalcogens 169
3.3.1 Introduction 169
3.3.2 Structural and Spectroscopic Properties 170
3.3.3 Syntheses 181
3.3.4 Reactivities 184
References 186
Chapter 4 Recent Developments in Chalcogen–Nitrogen Chemistry 191
Tristram Chivers and Risto Laitinen
4.1 Introduction 191
x Contents
4.2 Binary Chalcogen–Nitrogen Systems 192
4.2.1 Neutral Molecules 192
4.2.2 Binary Chalcogen Azides 197
4.2.3 Cations and Anions 198
4.3 Metal Complexes of Binary Chalcogen–Nitrogen
Anions 200
4.4 Cyclic Chalcogen Imides 201
4.5 Acyclic Organic Chalcogen–Nitrogen Compounds 203
4.5.1 Organochalcogen Azides 203
4.5.2 Organochalcogen(IV) Imides and Diimides 203
4.5.3 Organochalcogenylamines (N-Sulfinylamines)
RNSO 207
4.5.4 Chalcogen–Nitrogen Chains 207
4.5.5 S–Nitrosothiols 208
4.6 Chalcogen–Nitrogen-Carbon Ring Systems 210
4.6.1 Five-Membered Rings 210
4.6.2 Six-Membered Rings 218
4.6.3 Eight-Membered Rings 221
4.6.4 Metal Complexes 222
4.7 Chalcogen–Nitrogen–Phosphorus Ring Systems 223
4.8 N-Donor-Stabilized Chalcogen Cations 225
4.9 Summary and Outlook 229
References 230
Chapter 5 Chalcogen–Phosphorus (and Heavier Congener)
Compounds 238
Rob Davies and Laura Patel
5.1 Introduction 238
5.2 Preparation, Characterization, and Properties of
Compounds Containing Phosphorus–Chalcogen
Bonds 240
5.2.1 Phosphorus Chalcogenides [P E ] and
n m
Chalcogeno-Phosphate Anions [P E ]z(cid:2) 240
n m
5.2.2 Tertiary Phosphine Chalcogenides [R PE] 243
3
5.2.3 Diphosphine Di- and Monochalcogenides
[R P(E)-R0-P(E)R and R P(E)-R0-PR ] 245
2 2 2 2
5.2.4 Secondary Phosphine Chalcogenides
[R P(E)H] 248
2
5.2.5 Dichalcogenophosphinic Acids (R PE H)
2 2
and Their Derivatives 250
5.2.6 Trichalcogenophosphonic Acids (RPE H )
3 2
and Their Derivatives 253
5.2.7 Amido and Imido Derivatives of
Chalcogeno-Phosphorus Acids 255
