Table Of ContentE F F I C I E N T M E T H O D S
F O R P R E P A R I N G
S I L I C O N C O M P O U N D S
EDITED BY
HERBERT W. ROESKY
Institute of Inorganic Chemistry, University of G€ottingen, G€ottingen, Germany
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LIST OF CONTRIBUTORS
S.U. Ahmad
DepartmentofChemistry,TechnischeUniversita¨tBerlin,Berlin,Germany
R. Azhakar
InstituteofInorganicChemistry,UniversityofGo¨ttingen,Go¨ttingen,Germany
A. Baceiredo
Laboratoired’He´te´rochimieFondamentaleetApplique´e,Universite´ deToulouse,UPSandCNRS,Toulouse,
France
S.A. Baer
AnorganischeChemie,FluorchemiePhilipps-Universita¨tMarburg,Marburg,Germany
T. Böttcher
Institutfu¨rAnorganischeundAnalytischeChemie,Albert-Ludwigs-Universita¨tFreiburg,Albertstr.Freiburgi.Br.,
Germany
X. Chen
UniversityofColoradoatBoulder,Boulder,CO,UnitedStates
Y. Chujo
DepartmentofPolymerChemistry,GraduateSchoolofEngineering,KyotoUniversity,Kyoto,Japan
C. Cui
StateKeyLaboratoryofElemento-OrganicChemistry,NankaiUniversity,CollaborativeInnovationCenterof
ChemicalScienceandEngineering(Tianjin),Tianjin,China
P. Ducos
UniversityofBordeaux,InstituteofMolecularSciences,Talence,France
B. Dudziec
DepartmentofOrganometallicChemistry,AdamMickiewiczUniversityinPoznan,Poznan,Poland
M. Dutkiewicz
CenterforAdvancedTechnologies,AdamMickiewiczUniversityinPoznan,Poznan,Poland
H.A. Fogarty
UniversityofColoradoatBoulder,Boulder,CO,UnitedStates
A. Franczyk
CenterforAdvancedTechnologies,AdamMickiewiczUniversityinPoznan,Poznan,Poland
xx LISTOFCONTRIBUTORS
M. Grübel
DepartmentofChemistry,TechnischeUniversita¨tMu¨nchen,Garching,Germany
H. Hashimoto
TohokuUniversity,GraduateSchoolofScience,DepartmentofChemistry,Sendai,Japan
S.U.H. Heidsieck
DepartmentofChemistry,TechnischeUniversita¨tMu¨nchen,Garching,Germany
S. Inoue
DepartmentofChemistry,CatalysisResearchCenterandInstituteofSiliconChemistry,TechnischeUniversita¨t
Mu¨nchen,Garching,Germany
A. Jana
TataInstituteofFundamentalResearch,CentreforInterdisciplinarySciences,Narsingi,Hyderabad,India
T. Kato
Laboratoired’He´te´rochimieFondamentaleetApplique´e,Universite´ deToulouse,UPSandCNRS,Toulouse,
France
A. Kawachi
DepartmentofChemistry,GraduateSchoolofScience,HiroshimaUniversity,Kagamiyama,Higashi-Hiroshima,
Japan
S. Khan
DepartmentofChemistry,IndianInstituteofScienceEducationandResearch,Pashan,Pune,India
F. Kraus
AnorganischeChemie,FluorchemiePhilipps-Universita¨tMarburg,Marburg,Germany
E. Kroke
TUBergakademieFreiberg(TUBAF),InstituteforInorganicChemistry,LeipzigerStraße,Freiberg,Germany
S. Kyushin
DivisionofMolecularScience,FacultyofScienceandTechnology,GunmaUniversity,Kiryu,Gunma,Japan
Y. Landais
UniversityofBordeaux,InstituteofMolecularSciences,Talence,France
N.F. Lazareva
A.E.FavorskyIrkutskInstituteofChemistry,SiberianBranchoftheRussianAcademyofSciences,Favorsky,
Irkutsk,RussianFederation
K. Lou
StateKeyLaboratoryofElemento-OrganicChemistry,NankaiUniversity,Tianjin,China
B. Marciniec
CenterforAdvancedTechnologies,AdamMickiewiczUniversityinPoznan,Poznan,Poland
LISTOF CONTRIBUTORS xxi
J. Michl
UniversityofColoradoatBoulder,Boulder,CO,UnitedStates;InstituteofOrganicChemistryandBiochemistry,
AcademyofSciencesoftheCzechRepublic,Prague,CzechRepublic
R. Mirgalet
Laboratoired’He´te´rochimieFondamentaleetApplique´e,Universite´ deToulouse,UPSandCNRS,Toulouse,
France
A.M. Muzafarov
A.N.NesmeyanovInstituteofOrganoelementCompoundsofRussianAcademyofSciences(INEOSRAS),
Moscow,Russia
R. Pietschnig
UniversityKassel,DepartmentofChemistry,Kassel,Germany
B. Rieger
DepartmentofChemistry,TechnischeUniversita¨tMu¨nchen,Garching,Germany
U. Ritter
InstituteofInorganicChemistry,UniversityofGo¨ttingen,Go¨ttingen,Germany
F. Robert
UniversityofBordeaux,InstituteofMolecularSciences,Talence,France
H.W. Roesky
InstituteofInorganicChemistry,UniversityofGo¨ttingen,Go¨ttingen,Germany
G.-V. Röschenthaler
DepartmentofLifeSciencesandChemistry,JacobsUniversityBremengGmbH,Bremen,Germany
D. Scheschkewitz
ChairinGeneralandInorganicChemistry,SaarlandUniversity,Saarbru¨cken,Germany
H. Schmidbaur
DepartmentChemie,TechnischeUniversita¨tMu¨nchen,Garching,Germany
H.-G. Schmidt
InstituteofInorganicChemistry,UniversityofGo¨ttingen,Go¨ttingen,Germany
U. Schubert
ViennaUniversityofTechnology,InstituteofMaterialsChemistry,Vienna,Austria
S.S. Sen
CSIR-NationalChemicalLaboratory,Pashan,Pune,India
V.F. Sidorkin
A.E.FavorskyIrkutskInstituteofChemistry,SiberianBranchoftheRussianAcademyofSciences,Favorsky,
Irkutsk,RussianFederation
xxii LISTOFCONTRIBUTORS
K. Tanaka
DepartmentofPolymerChemistry,GraduateSchoolofEngineering,KyotoUniversity,Kyoto,Japan
R. Tanaka
InorganicMaterialChemistryGroup,SagamiChemicalResearchInstitute,Ayase,Kanagawa,Japan
H. Tobita
TohokuUniversity,GraduateSchoolofScience,DepartmentofChemistry,Aramaki,Aoba-ku,Sendai,Japan
M. Tretiakov
InstituteofInorganicChemistry,UniversityofGo¨ttingen,Go¨ttingen,Germany
M. Unno
DepartmentofChemistryandChemicalBiology,FacultyofScienceandTechnology,GunmaUniversity,Japan
B. Wang
UniversityofColoradoatBoulder,Boulder,CO,UnitedStates
N. Winkhofer
InstituteofInorganicChemistry,UniversityofGo¨ttingen,Go¨ttingen,Germany
Y. Wu
StateKeyLaboratoryofElemento-OrganicChemistry,NankaiUniversity,Tianjin,China
_
P. Zak
DepartmentofOrganometallicChemistry,AdamMickiewiczUniversityinPoznan,Poznan,Poland
J. Zech
DepartmentChemie,TechnischeUniversita¨tMu¨nchen,Garching,Germany
PREFACE
Naturehasalwayslookedlikeahorriblemass,butaswego
along we see patterns and put theory together,a certain
clarity comes and things get simpler.
RichardP.Feynman
The minerals in the earth’s crust are those resources which we
useforconstructingourtechnicalworld.Theelementsilicon,the
sister element of carbon, is the second most abundant element
after oxygen in the earth’s crust. Therefore silicon is an ubiq-
uitouselementandaninterestingresourcefornewapplications.
However, the most abundant silicon-containing minerals
are sand and silicates. The preparation of silicon from these
minerals uses high energyeconsuming processes to produce
verypureelementalsilicon.Toachieveasustainableproduction
line of silicon in this important field of chemistry, alternative
routes have to be developed.
“Sustainablechemistryisthedesign,manufacture,anduseof
environmentally benign chemical products and processes to
prevent pollution, produce less hazardous waste, and reduce
environmental and human health risks”. (Proceedings of the
OECDworkshoponsustainablechemistry,part3,Venice,October
15e17, 1998.)
Indeed, this terminology has in many cases of chemistry
already been fulfilled although further discussions and refine-
ment are still going on.
The collection of experiments from chemists around the
globe illustrates the broad and rich principles of silicon chem-
istry. All are educators and want to share their knowledge and
passion for silicon chemistry. I am very thankful for their won-
derful contributions. The authors of these experiments have
taken great care to describe the equipment and nature of the
substances employed; however, as with all chemical experi-
ments, care should be taken in handling hazardous materials in
an appropriate manner in a well-ventilated hood. The experi-
ments are intended for advanced students working in a safe
laboratory environment under qualified supervision.
Herbert W. Roesky
1
ARYLSILANES AS PRECURSORS
OF CYCLOHEXA-2,5-
DIENYLSILANES
Y. Landais
UniversityofBordeaux,InstituteofMolecularSciences,Talence,France
CHAPTER OUTLINE
Preparation ofcyclohexa-2,5-dienyldimethylsilanol 2
References 4
The Birch reduction of arenes is a well-known method to access
functionalized cyclohexadienes using lithium, sodium, or potas-
sium in ammonia as a reducing medium (1). This process has
beenappliedtoalargenumberofarenesandpolyarenes,including
aromaticcompounds substituted with a silicon group(2). Eaborn
first applied the Birch reduction to simple trialkylarylsilanes,
obtaining the desired silyl-substituted cyclohexa-2,5-dienes (3,4).
We extended to arylchlorosilanes this Birch reduction (5). The
resulting silanol, which is obtained, may be manipulated further,
forinstance,throughtheformationofasiloxane,allowingfurther
intramolecular hydrosilylation (6) or may be oxidized into a
hydroxy group following the TamaoeKumadaeFleming process
(7e9). The method can be extended to other chlorosilanes, but
steric hindrance around the silicon center is detrimental to the
yieldinsilanol.
Preparation of such silyl-substituted cyclohexa-2,5-dienes
may also be carried out as described by Woerpel through the
metallation of the parent cyclohexa-2,5-diene with t-BuLi fol-
lowed by the silylation of the resulting pentadienyl anion with
thesuitablechlorosilane(10).Wehavealsodevelopedanalterna-
tive electrochemical method (vide infra) using a sacrificial
aluminum anode (4,5,11).
EfficientMethodsforPreparingSiliconCompounds.http://dx.doi.org/10.1016/B978-0-12-803530-6.00001-9 1
Copyright©2016ElsevierInc.Allrightsreserved.
2 Chapter 1 ARYLSILANESASPRECURSORSOF CYCLOHEXA-2,5-DIENYLSILANES
Preparation of cyclohexa-2,5-dienyldimethylsilanol
Apparatus
A dry 250-mL three-necked flask equipped with a magnetic stir-
rer, an inlet for argon, a low-temperature thermometer, a gas
condenser cooled with liquid nitrogen, safety glasses, laboratory
coat, and protective gloves.
Chemicals
Ammonia gas cylinder, lithium powder. PhMe SiCl is commer-
2
cially available but may also be prepared on 200e300g scale
from bromobenzeneand Me SiCl (12).
2 2
Experimentalprocedure
In a dry 250-mL three-necked flask, equipped with a magnetic
stirrer, an inlet for argon, and a thermometer, was condensed
NH (80mL) at (cid:1)80(cid:3)C under argon. The phenyldimethylchloro-
3
silane(1mL,6mmol)wasthenslowlyaddedandawhiteprecip-
itateappeared.After5min,lithiumpowder(0.3g,42mmol)was
introducedandthesolutionturnedimmediatelyblue.Thissolu-
tion was thenstirredat(cid:1)80(cid:3)C for45min andanhydrousNH Cl
4
was added until the blue coloration disappears. Ether (30mL)
and water (20mL) were then added successively and ammonia
was evaporated at room temperature. The aqueous layer was
extracted with ether. The combined extracts were washed with
water (2(cid:4)) then with a saturated NaCl solution, dried over
MgSO , and the solvents were evaporated in vacuo. The residue
4
was then purified by Kugelrohr distillation (70(cid:3)C, 0.4mbar) or
by flash chromatography through Florisil (petroleum ether/
EtOAc 95:5) to give the cyclohexadienylsilanol as a colorless oil
(0.72g, 77%).
