The Development of the Chemistry of Silicon Compounds in Unusual Coordination States

Información del proyecto

Identificador del acuerdo de subvención: INTAS-RFBR95-0070

Fecha de inicio

Fecha de finalización

Financiado con arreglo a

• International Association for the promotion of cooperation with scientists from the independent states of the former Soviet Union (INTAS), 1993-

Coste total

Sin datos

Aportación de la UE

Sin datos

Coordinado por

Humboldt-Universität zu Berlin
Germany

Objetivo

The project is directed to the development of the fundamentals of the chemistry of organic derivatives of doubly bonded and hypervalent silicon as well as those containing doubly bonded silicon stabilized by coordination. It combines facilities and expertise of the lead groups which are individually very active in synthesis, physical methods and kinetics to make this collaboration particularly attractive for the achieving the following objectives:

(i) UV spectroscopic measurements and kinetic, and thermochemical identification of the unstable intermediates in the gas phase formed by thermal [4-2+2] cyclodecomposition of silacyclobutanes compressed in a free piston system. This part of the project is directed towards the elucidation of the detailed mechanism of the key reaction generating transient silenes through experimental observation giving kinetic and thermochemical identification of the primary and secondary intermediates, such as 1,4-biradicals, silenes, silylenes etc.

(ii) New approaches to the generation of silanones at normal and moderate temperatures. These will be (a) reaction of siloxanes and their C-functional derivatives with gallium or indium halogenides, (b) reaction of chlorosilanes (including hypervalent ones) with dimethylsulfoxide, pyridine-N-oxide, triethylphosphinoxide, some metal oxides of high redox potential, and salts, (c) autodecay of organosilicon compounds containing XSiOM (M=Si, O, N, S etc; X=Hal), (d) decomposition of dimethylsilyl esters of dicarbonic acids.

(iii) Synthesis of hypervalent (and pro-chelate) 1-silacyclobutanes, their ring-opening polymerization and thermal generation of silenes stabilized by intramolecular coordination. The principles of donor stabilization of silenes generated by thermal decomposition of the appropriate hypervalent (and pro-chelate) precursors will be applied to obtain silenes stable above 77 K which are of great interest for cryochemistry. Also, ring-opening polymerization of hypervalent 1-silacyclobutanes will be studied to create heterochain polycarbosilanes containing hypervalent silicon. 1-Methyl- and 1-chloromethyl-1-chloro-1-silacyclobutanes as well as 1,1-dichloro-1-silacyclobutane will be used as starting materials to be transformed into 2-aminoalkoxy-, 2-aminodialkoxy-, amido-N-methyl-, lactamo-N-methyl-, and ureido-N-methyl-derivatives. The synthesis and structural study of bis-N,N'-(1-silacyclobut-1-yl)methylated ureas and bis-N,N-(1-silacyclobut-1-yl)methylamides has high prority since those compounds have nanotechnological interest. They may form the basis of molecular switches and similar dynamic devices at single molecular level. The diverse proposals have the common theme of the development of the coordination chemistry and its direction to novel and potentially useful applications. The expected basic results of the research will be published in the scientific journals, e.g. J. Chem. Soc., J. Organometal. Chem., Organometallics, Russian Chem. Bull., etc.

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Programa(s)

• IC-INTAS - International Association for the promotion of cooperation with scientists from the independent states of the former Soviet Union (INTAS), 1993-

Tema(s)

• 3 - Chemistry

Convocatoria de propuestas

Datos no disponibles

Régimen de financiación

Datos no disponibles

Coordinador

Humboldt-Universität zu Berlin

• Aportación de la UE: Sin datos
• Dirección: 10115 Berlin ; Alemania
• Coste total: Sin datos

Participantes (1)

Russian Academy of Sciences

Rusia

• Aportación de la UE: Sin datos
• Dirección: 17912 Moscow
• Coste total: Sin datos