← Back to Search
Multifunctional Silicon Surfaces: Reaction Of Dichlorocarbene Generated From Seyferth Reagent With Hydrogen-terminated Silicon (111) Surfaces.
W. Liu, I. Sharp, T. Tilley
Published 2014 · Chemistry, Medicine
Download PDFAnalyze on Scholarcy
Insertion of dichlorocarbene (:CCl2), generated by decomposition of the Seyferth reagent PhHgCCl2Br, into the Si-H bond of a tertiary silane to form a Si-CCl2H group is an efficient homogeneous, molecular transformation. A heterogeneous version of this reaction, between PhHgCCl2Br and a silicon (111) surface terminated by tertiary Si-H bonds, was studied using a combination of surface-sensitive infrared and X-ray photoelectron spectroscopies. The insertion of dichlorocarbene into surface Si-H bonds parallels the corresponding reaction of silanes in solution, to produce surface-bound dichloromethyl groups (Si-CCl2H) covering ∼25% of the silicon surface sites. A significant fraction of the remaining Si-H bonds on the surface was converted to Si-Cl/Br groups during the same reaction, with PhHgCCl2Br serving as a halogen atom source. The presence of two distinct environments for the chlorine atoms (Si-CCl2H and Si-Cl) and one type of bromine atom (Si-Br) was confirmed by Cl 2p, Br 3d, and C 1s X-ray photoelectron spectroscopy. The formation of reactive, halogen-terminated atop silicon sites was also verified by reaction with sodium azide or the Grignard reagent (CH3MgBr), to produce Si-N3 or Si-Me functionalities, respectively. Thus, reaction of a hydrogen-terminated silicon (111) surface with PhHgCCl2Br provides a facile route to multifunctional surfaces possessing both stable silicon-carbon and labile silicon-halogen sites, in a single pot synthesis. The reactive silicon-halogen groups can be utilized for subsequent transformations and, potentially, the construction of more complex organic-silicon hybrid systems.
This paper references
Wet chemical routes to the assembly of organic monolayers on silicon surfaces via the formation of Si-C bonds: surface preparation, passivation and functionalization.
S. Ciampi (2010)
Highly stable organic monolayers for reacting silicon with further functionalities: the effect of the C-C bond nearest the silicon surface.
S. R. Puniredd (2008)
Thermal and Photoinduced Covalent Attachment of 3-Chloro-1-propanol on Si(100)-2×1
Y. Shao (2010)
How do electronic carriers cross Si-bound alkyl monolayers?
A. Salomon (2005)
A new method to generate arene-terminated Si(111) and Ge(111) surfaces via a palladium-catalyzed arylation reaction.
Y. Yamanoi (2012)
Mild and efficient functionalization of hydrogen-terminated Si(111) via sonochemical activated hydrosilylation.
Y. Zhong (2011)
Chemical and electrical passivation of Si(1 1 1) surfaces
Fangyuan Tian (2012)
Photoactivated Preparation and Patterning of Self-Assembled Monolayers with 1-Alkenes and Aldehydes on Silicon Hydride Surfaces.
F. Effenberger (1998)
Matrix-isolation study of the pyrolysis of bromochloromethyl-substituted organomercury compounds. Infrared spectra of the bromochlorocarbene andree radicals CCl2Br and CClBr2
A. K. Mal'tsev (1971)
Synthesis and Characterization of DNA-Modified Silicon (111) Surfaces
T. Strother (2000)
Covalent attachment of acetylene and methylacetylene functionality to Si(111) surfaces: scaffolds for organic surface functionalization while retaining Si-C passivation of Si(111) surface sites.
Patrick T. Hurley (2006)
Highly stable organic modification of Si(111) surfaces: towards reacting Si with further functionalities while preserving the desirable chemical properties of full Si-C atop site terminations.
S. R. Puniredd (2008)
Halomethyl-metal compounds X. The reaction of organosilicon, organogermanium and organotin hydrides with phenyl(trihalomethyl)mercury compounds☆
D. Seyferth (1967)
Bromine functionalized molecular adlayers on hydrogen passivated silicon surfaces
R. Basu (2006)
LEWIS ACID MEDIATED FUNCTIONALIZATION OF POROUS SILICON WITH SUBSTITUTED ALKENES AND ALKYNES
J. Buriak (1998)
Alkyl Monolayers on Silicon Prepared from 1-Alkenes and Hydrogen-Terminated Silicon
M. R. Linford (1995)
Heck coupling of olefins to mixed methyl/thienyl monolayers on Si(111) surfaces.
Leslie E. O'Leary (2013)
Insights into the Formation Mechanisms of Si−OR Monolayers from the Thermal Reactions of Alcohols and Aldehydes with Si(111)−H1
R. Boukherroub (2000)
Azidation of silicon(111) surfaces.
Peigen Cao (2008)
Photoreactivity of Unsaturated Compounds with Hydrogen-Terminated Silicon(111)
R. Cicero (2000)
Stable scaffolds for reacting Si nanowires with further organic functionalities while preserving Si-C passivation of surface sites.
O. Assad (2008)
Rate constants for the reactions of tris(trimethylsilyl)silyl radicals with organic halides
C. Chatgilialoglu (1989)
Attenuated total reflection Fourier transform infrared spectroscopy study of the adsorption of organic contaminants on a hydrogen-terminated Si(111) surface in air
S. Ye (1999)
Silicon surface functionalization targeting Si-N linkages.
F. Tian (2013)
Evidence for initiation of thermal reactions of alkenes with hydrogen-terminated silicon by surface-catalyzed thermal decomposition of the reactant.
T. Mischki (2009)
High-performance photoelectrochemical cells from ionic liquid electrolyte in methyl-terminated silicon nanowire arrays.
X. Shen (2010)
Formation of Covalently Attached Polymer Overlayers on Si(111) Surfaces Using Ring-Opening Metathesis Polymerization Methods
Agnes Juang (2001)
Photopatterned Hydrosilylation on Porous Silicon.
M. P. Stewart (1998)
Comparing the reactivity of alkynes and alkenes on silicon (100) surfaces.
A. Ng (2009)
Exciton-mediated hydrosilylation on photoluminescent nanocrystalline silicon.
M. P. Stewart (2001)
Halomethyl-metal compounds XX. An improved synthesis of phenyl(trihalomethyl)mercury compounds
D. Seyferth (1969)
Organometallic chemistry on silicon and germanium surfaces.
J. Buriak (2002)
Synthesis of gem-difluorinated cyclopropanes and cyclopropenes: trifluoromethyltrimethylsilane as a difluorocarbene source.
F. Wang (2011)
Functionalization of Semiconductor Surfaces: Tao/Semiconductor Surfaces
F. Tao (2012)
Passivation and Secondary Functionalization of Allyl-Terminated Si(111) Surfaces
Katherine E. Plass (2008)
Toward metal-organic insulator-semiconductor solar cells, based on molecular monolayer self-assembly on n-Si
Rotem Har-lavan (2009)
Molecular Spectroscopy by Means of ESCA III. Carbon compounds
U. Gelius (1970)
Covalent Bond Formation to a Carbon Nanotube Metal
K. Kamarás (2003)
Highly Stable Si−C Linked Functionalized Monolayers on the Silicon (100) Surface
A. Sieval (1998)
High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces.
L. Webb (2005)
Direct covalent grafting of conjugated molecules onto Si, GaAs, and Pd surfaces from aryldiazonium salts.
M. P. Stewart (2004)
Molecules on si: electronics with chemistry.
A. Vilan (2010)
Molecular engineering of semiconductor surfaces and devices.
G. Ashkenasy (2002)
Dehydrative cyclocondensation reactions on hydrogen-terminated Si(100) and Si(111): an ex situ tool for the modification of semiconductor surfaces.
T. R. Leftwich (2008)
Lewis Acid Mediated Hydrosilylation on Porous Silicon Surfaces
J. Buriak (1999)
Azide-modified graphitic surfaces for covalent attachment of alkyne-terminated molecules by "click" chemistry.
Anando Devadoss (2007)
Comparison of the Photoelectrochemical Behavior of H‑Terminated and Methyl-Terminated Si(111) Surfaces in Contact with a Series of One-Electron, Outer-Sphere Redox Couples in CH_3CN
Ronald L. Grimm (2012)
Halomethylmetal compounds. XVII. The mechanism of dichlorocarbene insertion into the Si-H bond by the mercurial route
D. Seyferth (1968)
Sidewall functionalization of single-walled carbon nanotubes by addition of dichlorocarbene.
H. Hu (2003)
Alkylation of Si Surfaces Using a Two-Step Halogenation/Grignard Route
A. Bansal (1996)
Infrared spectroscopy study of initial stages of oxidation of hydrogen‐terminated Si surfaces stored in air
M. Niwano (1994)
Functionalization of Azide-Terminated Silicon Surfaces with Glycans Using Click Chemistry: XPS and FTIR Study
A. C. Gouget-Laemmel (2013)
Hybrids of organic molecules and flat, oxide-free silicon: high-density monolayers, electronic properties, and functionalization.
Y. Li (2012)
Covalently attached monolayers on crystalline hydrogen-terminated silicon: extremely mild attachment by visible light.
Qiao-yu Sun (2005)
Infrared and X-ray Photoelectron Spectroscopic Studies of the Reactions of Hydrogen-Terminated Crystalline Si(111) and Si(100) Surfaces with Br2, I2, and Ferrocenium in Alcohol Solvents
J. Haber (2002)
The Preparation of Dihalomethyl Derivatives of Carbon, Silicon, and Germanium by the Action of Phenyl-(trihalomethyl)mercurials on C-H, Si-H, and Ge-H Linkages
D. Seyferth (1963)
This paper is referenced by
Catching Elusive 2‐Furyl Carbenes with Silanes: A Metal‐Free Microwave‐Assisted Silicon‐Hydrogen Bond Functionalization
Silvia González-Pelayo (2016)
Efficient Electrochemical and Photoelectrochemical H2 Production from Water by a Cobalt Dithiolene One-Dimensional Metal-Organic Surface.
Courtney A. Downes (2015)
Surface chemistry of N-Heterocyclic carbenes and the self-assembly, structure, and properties of polymer metal-organic cage gels
A. Zhukhovitskiy (2016)
Carbene Ligands in Surface Chemistry: From Stabilization of Discrete Elemental Allotropes to Modification of Nanoscale and Bulk Substrates.
A. Zhukhovitskiy (2015)
Fifty Years of Hydrosilylation in Polymer Science: A Review of Current Trends of Low-Cost Transition-Metal and Metal-Free Catalysts, Non-Thermally Triggered Hydrosilylation Reactions, and Industrial Applications
Robin Hofmann (2017)
Control of band structure of van der Waals heterostructures: Silicene on ultrathin silicon nanosheets
S. Li (2014)
Reactions of Persistent Carbenes with Hydrogen-Terminated Silicon Surfaces.
A. Zhukhovitskiy (2016)