Derivatization of surfaces via reaction of strained silicon-carbon bonds: characterization by photoacoustic spectroscopy

Journal Article · Fri Oct 26 04:00:00 EDT 1979 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/ja00516a003· OSTI ID:5740463

Fischer, A B; Kinney, J B; Staley, R H; Wrighton, M S

Ferrocene-centered reagents can be bound to the surface of high surface area (400 m/sup 2//g) silica by reaction of the silica with alkane solutions of (1,1'-ferrocenediyl)dichlorosilane (Ia), (1,1'-ferrocenediyl)dimethylsilane (Ib), or (1,1'-ferrocenediyl)diphenylsilane (Ic). Derivatization is not found when ferrocene itself is used as the derivatization reagent; ferrocene is easily washed from the silica powder by solvents which do not affect the ferrocene centers bound upon reaction of the silica with Ia-c. As determined by photoacoustic spectroscopy, derivatization with Ia-c results in ring opening of the strained C-Si-C linkage bridging the two cyclopentadienyl rings to yield a simple, monosubstituted ferrocene center attached to the surface. Surface -OH functionality apparently reacts in a manner analogous to homogeneous solution sources of -OH such as MeOH. Reaction of Ib with MeOD yields (Fe(eta/sup 5/-C/sub 5/H/sub 4/D)(eta/sup 5/-C/sub 5/H/sub 4/Si(OMe)Me/sub 2/)). Optical absorption spectral changes accompanying reaction of Ia-c with solution sources of -OH are consistent with the differences found in the photoacoustic spectra of the pure powders of Ia-c compared to the silica powders derivatized with these reagents. Reaction of silica powders derivatized with Ia-c with acidic solutions of benzoquinone results in the oxidation of the surface-confined ferrocene centers to ferricenium centers giving photoacoustic spectra nearly the same as that from an authentic sample of a pure ferricenium salt. The surface-confined ferricenium can be used to oxidize N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) to TMPD/sup +/. in solution; this reaction allows an estimate of the surface coverage at 10/sup -11/ mol/cm/sup 2/. 3 figures, 2 tables.

• Research Organization: Massachusetts Inst. of Tech., Cambridge
• OSTI ID: 5740463
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 44:22; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ALCOHOLS
ALKANES
AROMATICS
BENZOQUINONES
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLOROFORM
COMPLEXES
DATA
DATA FORMS
DEUTERIUM COMPOUNDS
DIENES
EXPERIMENTAL DATA
HALOGENATED ALIPHATIC HYDROCARBONS
HEXANE
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
INFRARED SPECTROMETERS
IRON COMPLEXES
ISOLATED VALUES
MAGNETIC RESONANCE
MASS SPECTRA
MEASURING INSTRUMENTS
METHANOL
MINERALS
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOACOUSTIC SPECTROMETERS
POLYENES
POWDERS
QUINONES
RESONANCE
SILANES
SILICA
SILICON COMPOUNDS
SILICON OXIDES
SPECTRA
SPECTROMETERS
SURFACE AREA
SURFACE PROPERTIES
TOLUENE
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET SPECTRA
WATER