Low-coordinate Organosilicon Chemistry: Fundamentals, Excursions Outside the Field, and Potential Applications

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Alvi, Muhammad Rouf,1980-Uppsala universitet,Fysikalisk-organisk kemi,Henrik Ottosson (författare)

Low-coordinate Organosilicon Chemistry : Fundamentals, Excursions Outside the Field, and Potential Applications

BokEngelska2012

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Uppsala :Acta Universitatis Upsaliensis,2012
75 s.
electronicrdacarrier

Nummerbeteckningar

LIBRIS-ID:oai:DiVA.org:uu-169796
ISBN:9789155482961
https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-169796URI

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Språk:engelska
Sammanfattning på:engelska

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Serie

Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology,1651-6214 ;907

Anmärkningar

This thesis reports on unsaturated silicon compounds, as well as excursions from these into germanium chemistry, single molecule electronics, and silyl protective group chemistry. Both experimental and computational investigations were performed. Potassium germenolates were synthesized through reactions of tris(timethylsilyl) substituted acyl- and carbamylgermanes with potassium tert-butoxide. The potassium germenolates calculated by density functional theory have pyramidal structures at the Ge atoms, similar to the Si in the corresponding potassium silenolates, indicating negative charge on germanium rather than on oxygen. Germenolates also display germyl anion-like reactivity instead of germene-like reactivity as they are alkylated at Ge and initiate anionic polymerization of dienes rather than form [4+2] cycloadducts. The NMR chemical shifts reveal more negative charge at Ge in germenolates than at Si in analogous silenolates. Computations indicate that silabenzenes and silapyridines are reachable via [1,3]-silyl shifts from cyclic conjugated acylsilanes. Differently sized substituents were considered to prevent dimerizations, and 1-triisopropylsilyl-2-triisopropylsiloxy-6-tert-butylsilabenzene is a good synthetic target. Computations also show that silaphenolates are species with negative charge primarily localized at oxygen atom. Their planar structures, bond lengths, and NICS values reveal significant influence of aromaticity. Electrostatic repulsion should increase their stability, however, steric bulk is also important. Furthermore, it was found computationally that [1,3]-silyl shift from an acylsilane to a silene can function as a molecular switch reaction. Conductance calculations support this proposition. Finally, tris(trimethylsilyl)silylmethaneamide (hypersilylamide) together with catalytic amounts of triflic acid were found to be efficient for protection of a range of alkyl and aryl alcohols and thiols in good to excellent yields. The protocol can be used to protect the less hindered OH group of a diol and has a broad functional group tolerance. A catalytic cycle is proposed. Hypersilyl protected alcohols and thiols are deprotected efficiently under photolytic conditions.

Ämnesord och genrebeteckningar

NATURVETENSKAP Kemi Organisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Organic Chemistry hsv//eng
organosilicon
silene
silaaromatics
silenolate
hypersilyl group
alcohol protection
molecular switch
Kemi med inriktning mot organisk kemi
Chemistry with specialization in Organic Chemistry

Biuppslag (personer, institutioner, konferenser, titlar ...)

Ottosson, Henrik,DocentUppsala universitet,Fysikalisk-organisk kemi (preses)
Ohshita, Joji,ProfessorDepartment of Applied Chemistry, Graduate School of Engineering, Hiroshima University, (opponent)
Uppsala universitetFysikalisk-organisk kemi (creator_code:org_t)

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Av författaren/redakt...: Alvi, Muhammad R ...; Ottosson, Henrik ...; Ohshita, Joji, P ...

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NATURVETENSKAP: NATURVETENSKAP; och Kemi; och Organisk kemi

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Av lärosätet: Uppsala universitet

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