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A general method for the formation of acetals using chlorotrimethylsilane has been developed. Dioxolanes are formed from most carbonyl groups whereas methyl acetals are only formed from electron-poor carbonyl groups. The intermediacy of a silicon-bound carbonyl species is discussed. / The method has been extended to the formation of esters. In a solution of the alcohol to be esterified, methyl, ethyl, benzyl and 2-trimethylsilylethyl esters are readily formed in the presence of chlorotrimethylsilane. Using ('29)Si-N.M.R., a trimethylsilyl ester has been shown to be an intermediate in the reaction. / The Lewis acid catalyzed condensation of 1,3-bis-trimethylsiloxy-1-methoxy-1,3-butadiene with a variety of dielectrophiles, in a 1,2 relationship, has been investigated. The relative order of electrophilic reactivity towards this compound has been found to be; RR'C(Cl)SC(,6)H(,5) > ArCOCHO > ArCOCHO > RC(OCH(,3))(,2),RC(OCH(,3))SC(,6)H(,5) > RCHCl(,2). The dialkylation of 1,3-bis-trimethylsiloxy-1-methoxy-1,3-butadiene has been shown to lead to hydroxycyclopentenones with the same substitution pattern as the prostaglandins skeleton. Using ('29)Si-N.M.R., the mechanism of this reaction has been shown to proceed in two sequential steps; reaction of the (gamma)-position takes place first to give a titanium-bound intermediate, the thus formed intermediate then undergoes (alpha)-alkylation to give the cyclopentenone compound.

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No description available.

Marburg, Universiẗat, Diss., 1999.

Cellulose has emerged as an indispensable membrane material due to its abundant availability, low cost, fascinating physiochemical properties and environment benignancy. However, it is believed that the potential of this polymer is not fully explored yet due to its insolubility in the common organic solvents, encouraging the use of derivatization-regeneration method as a viable alternative to the direct dissolution in exotic or reactive solvents. In this work, we use trimethylsilyl cellulose (TMSC), a highly soluble cellulose derivative, as a precursor for the fabrication of cellulose thin film composite membranes. TMSC is an attractive precursor to assemble thin cellulose films with good deposition behavior and film morphology; cumbersome solvents used in the one step cellulose processing are avoided. This derivative is prepared from cellulose by the known silylation reaction. The complete transformation of TMSC back into cellulose after the membrane formation is carried out by vapor-phase acid treatment, which is simple, scalable and reproducible. This process along with the initial TMSC concentration determines the membrane sieving characteristics. Unlike the typical regenerated cellulose membranes with meso- or macropores, membranes regenerated from TMSC display micropores suitable for the selective separation of nanomolecules in aqueous and organic solvent nanofiltration. The membranes introduced in this thesis represent the first polymeric membranes ever reported for highly selective separation of similarly sized small organic molecules based on charge and size differences with outstanding fluxes. Owing to its strong hydrophilic and amorphous character, the membranes also demonstrate excellent air-dehumidification performance as compared to previously reported thin film composite membranes. Moreover, the use of TMSC enables the creation of the previously unfeasible cellulose–polydimethylsiloxane (PDMS) and cellulose–polyethyleneimine (PEI) blend membranes with a good compatibility. The cellulose–PDMS membranes demonstrate attractive performance in ethanol-water pervaporation as compared to the commercial PDMS membrane, and allow nanofiltration of a wide range of solvents with different polarity. The cellulose-PEI membranes exhibit anomalous performance improvement in nanofiltration as compared to the corresponding pure membranes. This study has opened up many great opportunities for cellulose to continuously contribute to sustainable and economical membrane processes.

The purpose of this investigation was to study the chemistry of the new and novel (trimethylsilyl)ketene. This ketene was synthesized by pyrolysis of (trimethylsilyl)ethoxyacetylene which was prepared from ethoxyacetylene and methyllithium. (Trimethylsilyl)ketene is a very stable and isolable ketene which does not dimerize and, therefore, provides an opportunity for some unique studies that have not been possible with other monosubstituted ketene.

In the organometallic chemistry, the imido complexes are an interesting species because it of their rich reactivity. Imido has two forms, where M=N-R form is nucleophilic and M¡ÝN-R form is elctrophilic. The thermo- or photochemical- decomposition of metal azido complexes is known to result in the formation of the corresponding metal nitride(M¡ÝN) or imido complexes. These reactions are oxidative cleavage type. As far as we know, imido species have not been generated on metal surfaces; therefore, we attempt to use the azidotrimethylsilane((CH3)3Si-N3 ; TMSN3) as precursors to produce imido species(TMSN=Cu) by N2 extrusion mechanism on Cu(111). The process was explored by a combination of temperature-programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and X-ray photoemission spectroscopy (XPS) techniques. In addition, density functional theory (DFT) calculations were conducted to obtain the optimized geometries for the various surface intermediates. The computed IR spectra facilitated the vibrational mode assignments. TPD spectra show that TMSN=Cu was hydrogenated to the TMSNH2 amine product around 520 K. We propose that the hydrogen source is adsorbed methyl groups, invoking the cleavage of the Si-C bond. TMSCH2N3 molecule was also investigated. In this case, N2 and H2 molecules were found to desorb around 260 K and 320K. A novel TMSC¡ÝN product was observed around 280K. We suggest it is a result of the metathesis reaction from ethylidyne (TMSC¡ÝCu) and nitride(N¡ÝCu) species. The TMSC¡ÝCu species are produced by double £\-hydride elimination of TMSCH2-Cu groups. The N¡ÝCu may be generated by the thermaldecomposition of copper azide(N=N=N-Cu). RAIRS reveal that there are three kinds of azido vibrations,where the higher frequency is assigned to the N=N=N-Cu species. This product is verified by the TPD of adsorbed TMSC¡ÝN molecule. Intriguingly, the thermal chemistry of TMSC¡ÝN molecule indicates that the isomeric molecule TMSN¡ÝC could be formed around 210 K, evidenced by a notable change in the RAIRS. The higher frequency £hC¡ÝN of TMSC¡ÝN transforms into a lower frequency £hC¡ÝN for TMSN¡ÝC. The coverage-dependent studies of RAIRS and XPS performed at 160 K surface temperature show that the isomerization may be intermolecular. The back-£k bonded TMSN¡ÝC molecule is desorbed around 410 K. XPS and RAIRS at 800 K show that isocyanide could polymerize to polyisocyanide, with an imine structure, and the characteristic C¡ÝN stretching mode disappeared.

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The reaction between pentacarbonylbis(trimethylsilyl)ethynetungsten(0), W(CO)5(&amp / #951 / 2-btmse), and triphenylbismuthine, Bi&Oslash / 3, yields pentacarbonyltriphenylbismuthinetungsten(0), W(CO)5(Bi&Oslash / 3), as the sole product. The kinetics of the substitution of btmse by Bi&Oslash / 3 was studied by means of quantitative FT-IR Spectroscopy. The starting complex was prepared photochemically from hexacarbonyltungsten, W(CO)6, in the presence of excess btmse in n-hexane and identified by FT-IR and NMR Spectroscopies. The substitution reactions were performed in cyclohexane solutions at different concentrations of both leaving and entering ligand to observe the dependence of observed rate constant, kobs, on the concentration of entering and leaving ligands and also, at different temperatures to evaluate the activation enthalpy (&amp / #8710 / H&amp / #8800 / ) and the activation entropy (&amp / #8710 / S&amp / #8800 / ). The IR extinction coefficients for CO stretching were determined for both the starting complex W(CO)5(&amp / #951 / 2-btmse), and the product W(CO)5(Bi&Oslash / 3). Quantitative IR Spectroscopy does not show any significant reduction in the total amount of substance (material balance). Formation of W(CO)6 (in small amount) was attributed to the decomposition of the product, W(CO)5Bi&Oslash / 3. From the evaluation of kinetic data, a mechanism was proposed in which the rate determining step is the cleavage of btmse ligand from the starting complex, W(CO)5(&amp / #951 / 2-btmse) and the formation of solvated complex, W(CO)5(solvent). Thus, the reaction is essentially dissociative. The large positive value of activation entropy (&amp / #8710 / S&amp / #8800 / ) and large value of activation enthalpy (&amp / #8710 / H&amp / #8800 / ) are indicative of a dissociative mechanism.