Multifunctional silicon surfaces: Reaction of dichlorocarbene generated from seyferth reagent with hydrogen-terminated silicon (111) surfaces

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.