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New organosilicon chemistry.

Gonzalez Navarro, Paulina Elena.

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New organosilicon chemistry.

Record Type:	Electronic resources : Monograph/item
Title/Author:	New organosilicon chemistry./
Author:	Gonzalez Navarro, Paulina Elena.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2016,
Description:	177 p.
Notes:	Source: Dissertation Abstracts International, Volume: 78-07(E), Section: B.
Contained By:	Dissertation Abstracts International78-07B(E).
Subject:	Organic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10246650
ISBN:	9781369522938

New organosilicon chemistry.
Gonzalez Navarro, Paulina Elena.

New organosilicon chemistry. - Ann Arbor : ProQuest Dissertations & Theses, 2016 - 177 p.

Source: Dissertation Abstracts International, Volume: 78-07(E), Section: B.

Thesis (Ph.D.)--The University of Texas at El Paso, 2016.

The formation of siloxymethylamine intermediates R3SiOCH 2NMe2, 1, as initial products of the reduction of DMF by hydrosilanes catalyzed by Mo(CO)5NMe3 has been reported. These siloxymethylamines can react with R'3SiH to form trimethylamine and disiloxanes, and with chlorosilanes to form disiloxanes and ClCH 2NMe2, Eschenmoser's salt. I shall illustrate, in Chapter 1, how attempts to react 1, formed in situ in the presence of chlorosilanes R'3SiCl in the hope producing heterosilyl disiloxanes, R3SiOSiR'3, was not successful but led to a newly discovered activation of the Si-Cl bond by DMF.

ISBN: 9781369522938Subjects--Topical Terms:

523952
Organic chemistry.

New organosilicon chemistry.
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020 $a 9781369522938
035 $a (MiAaPQ)AAI10246650
035 $a AAI10246650
040 $a MiAaPQ $c MiAaPQ
100 1 $a Gonzalez Navarro, Paulina Elena. $3 3290656
245 1 0 $a New organosilicon chemistry.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2016
300 $a 177 p.
500 $a Source: Dissertation Abstracts International, Volume: 78-07(E), Section: B.
500 $a Adviser: Keith H. Pannell.
502 $a Thesis (Ph.D.)--The University of Texas at El Paso, 2016.
520 $a The formation of siloxymethylamine intermediates R3SiOCH 2NMe2, 1, as initial products of the reduction of DMF by hydrosilanes catalyzed by Mo(CO)5NMe3 has been reported. These siloxymethylamines can react with R'3SiH to form trimethylamine and disiloxanes, and with chlorosilanes to form disiloxanes and ClCH 2NMe2, Eschenmoser's salt. I shall illustrate, in Chapter 1, how attempts to react 1, formed in situ in the presence of chlorosilanes R'3SiCl in the hope producing heterosilyl disiloxanes, R3SiOSiR'3, was not successful but led to a newly discovered activation of the Si-Cl bond by DMF.
520 $a In Chapter 2, we surmised that 1 acts as a transient siloxy-imminium ion pair [R3SiO]- [CH2NMe 2]+, and further suggested that these intermediates could be useful Mannich reagents, dimethylaminomethyl [Me2NCH2] transfer agents. Furthermore, I shall present the reactions between 1 and compounds with a series of E-H bonds (E = O, S, N) which prove its utility and reliability as a new [CH2NMe2] transfer reagent.
520 $a We have previously reported the formation of a series of group 14 substituted methanes, (R3E)nCH4-n (E = Si, Ge, Sn, Pb; R = combinations of methyl and aryl groups; n = 2,3,4). We also used these materials where an R group = C6H5 to form Cr(CO) 3 derivatives. During such studies we observed significant C-E bond cleavage products to form (R3E)n-1CH4-n products. It was proposed that the Cr(CO)3 substituent was responsible for this E-C bond activation. Now we have synthesized silicon and germanium homologous compounds with their Cr(CO)3 derivatives, and will study their hydrolytic stability, Chapter 3. Treatment of arenechromiumtricarbonyl complexes with regular n-Bu2O/THF will also be described to illustrate the potential activation of E-C bonds by the transition metal substituent.
590 $a School code: 0459.
650 4 $a Organic chemistry. $3 523952
690 $a 0490
710 2 $a The University of Texas at El Paso. $b Chemistry. $3 1672689
773 0 $t Dissertation Abstracts International $g 78-07B(E).
790 $a 0459
791 $a Ph.D.
792 $a 2016
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10246650