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Computational Inves...
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Alvi, Muhammad RoufUppsala universitet,Fysikalisk-organisk kemi
(författare)
Computational Investigation of Brook-Type Silabenzenes and Their Possible Formation through [1,3]-Si -> O Silyl Shifts
- Artikel/kapitelEngelska2013
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2012-12-18
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American Chemical Society (ACS),2013
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LIBRIS-ID:oai:DiVA.org:uu-169784
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https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-169784URI
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https://doi.org/10.1021/om300023sDOI
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Språk:engelska
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Sammanfattning på:engelska
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Ämneskategori:ref swepub-contenttype
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Ämneskategori:art swepub-publicationtype
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Quantum chemical calculations with the M062X hybrid meta density functional theory method were performed in order to examine formation of Brook-type silabenzenes 4a – 4l, silapyridines 6a – 6d, and five-membered ring silaheteroaromatics 8a – 8d through [1,3]-trimethylsilyl (TMS) and [1,3]-tri(isopropyl)silyl (TIPS) shifts from a tetrahedral silicon atom to an adjacent carbonyl oxygen of cyclic conjugated acylsilane precursors. All Brook-type silabenzenes and silapyridines, having a 2-trialkylsiloxy substituent, are at lower relative energies than their precursors, whereas silaheteroaromatics 8a – 8d are found at slightly higher energies. The free energies of activation for the thermal [1,3]-TMS shifts range from 29 to 44 kcal/mol, with the lowest for a Brook-type silapyridine and the highest for a silafuran. The geometries of the Brook-type silabenzenes, silapyridines, silafuran and silathiophene indicate aromatic character, but the silapyrroles are nonaromatic. At M062X/6-311+G(d)//M062X/6-31G(d) level all Brook-type silabenzene dimers studied herein are more stable than two silabenzenes, also for a silabenzene with bulky TIPS, OTIPS and tert-butyl substituents (4l). Yet, comparisons of the B3LYP/6-31G(d) dimerization energies of 4l with that of the isolable 1-Tbt-silabenzene (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl) of Tokitoh [J. Chin. Chem. Soc. 2008, 55, 487] indicate that 4l will also be a monomeric silabenzene, and thus, a suitable synthetic target.
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Burkhard O., JahnUppsala universitet,Institutionen för kemi - BMC
(författare)
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Ottosson, HenrikUppsala universitet,Fysikalisk-organisk kemi(Swepub:uu)heott255
(författare)
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Uppsala universitetFysikalisk-organisk kemi
(creator_code:org_t)
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Ingår i:Organometallics: American Chemical Society (ACS)32:1, s. 16-280276-73331520-6041
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