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The Synthesis and Reactivity of New ...

Melton, Christopher Edward.

The Synthesis and Reactivity of New m-Terphenyl Substituted Aluminum Hydrides and Aluminum Iodides.

Record Type:	Electronic resources : Monograph/item
Title/Author:	The Synthesis and Reactivity of New m-Terphenyl Substituted Aluminum Hydrides and Aluminum Iodides.
Author:	Melton, Christopher Edward.
Description:	208 p.
Notes:	Source: Dissertation Abstracts International, Volume: 75-10(E), Section: B.
Notes:	Adviser: Philip P. Power.
Contained By:	Dissertation Abstracts International75-10B(E).
Subject:	Organic chemistry.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3626905
ISBN:	9781321019698

The Synthesis and Reactivity of New m-Terphenyl Substituted Aluminum Hydrides and Aluminum Iodides.
Melton, Christopher Edward.

The Synthesis and Reactivity of New m-Terphenyl Substituted Aluminum Hydrides and Aluminum Iodides. - 208 p.

Source: Dissertation Abstracts International, Volume: 75-10(E), Section: B.

Thesis (Ph.D.)--University of California, Davis, 2014.

This item must not be sold to any third party vendors.

The synthetic utility of the m-terphenyl aluminum hydrides [ArMe6AlH2]2, [AriPr4AlH 2]2 and [AriPr8AlH2]2 have been investigated. (ArMe6 = 2,6-(2,4,6-Me3C 6H2)C6H5, AriPr4 = 2,6-(2,6- iPr2C6H3)C6H5, AriPr8 = 2,6-(2,4,6-iPr3C6H 2)-3,5-iPr2-C6H). The hydrides were found to react with terminal alkynes, RCCH (R = C6H5 , Me3Si) and alkenes (H2CCHR', R = C(CH3 )3, C6H5, H) but internal olefins did not react with the alanes. Comparison of reaction times between [Ar Me6AlH2]2, [AriPr4AlH2] 2 and [AriPr8AlH2]2 with alkenes display a positive correlation between the aluminum ligand size and reactivity. This was rationalized on the basis of an increase in monomeric aluminum species concentration due to increased steric bulk surrounding the aluminum center. [ArMe6AlH2]2, [AriPr4AlH 2]2 and [AriPr8AlH2]2 were used to form [ArMe6AlH(NH2)]2, [Ar iPr4AlH(NH2)]2 and [AriPr8AlH(NH 2)]2. [ArMe6AlH2]2 was mixed with excess PH3 to produce the new Lewis base and Lewis acid-free aluminum phosphides (ArMe6Al)4(PH2) 4(PH)2 and[(ArMe6Al)2PH2(PH)][(H 2P)3AlArMe6]. The bulky alanates [LiH 3AlR]n and [Li(L)H3AlR]n (R = Ar Me6, AriPr4, AriPr8, DEDA, DEDA = [DippNCH 2CH2NDipp]2-; L = THF, Et2O, NMe 3; n = 1,2) were used in metathesis reactions with a series of transition metal dihalides in a variety of solvents. It was found that coordinating and non-coordinating solvents produced metastable solutions, but that non-coordinating solvents deposited metal at a much slower rate. The synthesis and characterization of ethylene diamido aluminum derivatives [Li(THF)2H2Al(DEDA)] 2, (Me3N)HAl(DEDA), (Me3N)ClAl(DEDA) and I 2Al(DippNCHCHNDipp) were isolated and structurally characterized. The closed shell iodide (THF)IAl(DEDA) could not be crystallized, but its presence was confirmed by 1H NMR.

ISBN: 9781321019698Subjects--Topical Terms:

708640
Organic chemistry.

The Synthesis and Reactivity of New m-Terphenyl Substituted Aluminum Hydrides and Aluminum Iodides.
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020 $a 9781321019698
035 $a (MiAaPQ)AAI3626905
035 $a AAI3626905
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100 1 $a Melton, Christopher Edward. $3 708679
245 1 4 $a The Synthesis and Reactivity of New m-Terphenyl Substituted Aluminum Hydrides and Aluminum Iodides.
300 $a 208 p.
500 $a Source: Dissertation Abstracts International, Volume: 75-10(E), Section: B.
500 $a Adviser: Philip P. Power.
502 $a Thesis (Ph.D.)--University of California, Davis, 2014.
506 $a This item must not be sold to any third party vendors.
506 $a This item must not be added to any third party search indexes.
520 $a The synthetic utility of the m-terphenyl aluminum hydrides [ArMe6AlH2]2, [AriPr4AlH 2]2 and [AriPr8AlH2]2 have been investigated. (ArMe6 = 2,6-(2,4,6-Me3C 6H2)C6H5, AriPr4 = 2,6-(2,6- iPr2C6H3)C6H5, AriPr8 = 2,6-(2,4,6-iPr3C6H 2)-3,5-iPr2-C6H). The hydrides were found to react with terminal alkynes, RCCH (R = C6H5 , Me3Si) and alkenes (H2CCHR', R = C(CH3 )3, C6H5, H) but internal olefins did not react with the alanes. Comparison of reaction times between [Ar Me6AlH2]2, [AriPr4AlH2] 2 and [AriPr8AlH2]2 with alkenes display a positive correlation between the aluminum ligand size and reactivity. This was rationalized on the basis of an increase in monomeric aluminum species concentration due to increased steric bulk surrounding the aluminum center. [ArMe6AlH2]2, [AriPr4AlH 2]2 and [AriPr8AlH2]2 were used to form [ArMe6AlH(NH2)]2, [Ar iPr4AlH(NH2)]2 and [AriPr8AlH(NH 2)]2. [ArMe6AlH2]2 was mixed with excess PH3 to produce the new Lewis base and Lewis acid-free aluminum phosphides (ArMe6Al)4(PH2) 4(PH)2 and[(ArMe6Al)2PH2(PH)][(H 2P)3AlArMe6]. The bulky alanates [LiH 3AlR]n and [Li(L)H3AlR]n (R = Ar Me6, AriPr4, AriPr8, DEDA, DEDA = [DippNCH 2CH2NDipp]2-; L = THF, Et2O, NMe 3; n = 1,2) were used in metathesis reactions with a series of transition metal dihalides in a variety of solvents. It was found that coordinating and non-coordinating solvents produced metastable solutions, but that non-coordinating solvents deposited metal at a much slower rate. The synthesis and characterization of ethylene diamido aluminum derivatives [Li(THF)2H2Al(DEDA)] 2, (Me3N)HAl(DEDA), (Me3N)ClAl(DEDA) and I 2Al(DippNCHCHNDipp) were isolated and structurally characterized. The closed shell iodide (THF)IAl(DEDA) could not be crystallized, but its presence was confirmed by 1H NMR.
520 $a An optimization of the synthesis of Na2[ArMe6Al] 3 and Na2[AriPr4Al]2, showed that the main issue associated with the poor yields obtain for these compounds was the presence of chloride-containing impurities such as [AriPr4 AlMeCl]2, which do not lose chloride upon reduction with alkali metals. The new m-terphenyl aluminum species pI-AriPr4AlI 2 (pI-AriPr4 = 2,6-(2,6-iPr2C6H3)-4-IC6H2), Ar iPr8AlI2 and AriPr8AlMe2 were synthesized and structurally characterized. An extensive study of metathesis reactions between tungsten halide salts and m-terphenyl lithium salts was conducted, which suggested that m-terphenyl lithium reagents produce reduction at the metal center, but do not produce products which are amenable to structural characterization.
590 $a School code: 0029.
650 4 $a Organic chemistry. $3 708640
650 4 $a Molecular chemistry. $3 468169
650 4 $a Chemistry. $3 188628
690 $a 0490
690 $a 0431
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710 2 $a University of California, Davis. $b Chemistry. $3 708680
773 0 $t Dissertation Abstracts International $g 75-10B(E).
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791 $a Ph.D.
792 $a 2014
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3626905