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Chelating nitrogen-donor complexes o...

Fneich, Bassam N.

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Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper./
作者:	Fneich, Bassam N.
面頁冊數:	155 p.
附註:	Source: Dissertation Abstracts International, Volume: 67-09, Section: B, page: 5064.
Contained By:	Dissertation Abstracts International67-09B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3235940
ISBN:	9780542897740

Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper.
Fneich, Bassam N.

Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper. - 155 p.

Source: Dissertation Abstracts International, Volume: 67-09, Section: B, page: 5064.

Thesis (Ph.D.)--The University of Toledo, 2006.

Nitrogen-donor ligands play an important role in inorganic and organometallic chemistry. In general, the ligand design is typically tailored to address specific transformations. In particular, the interplay of electronics and sterics dictates the properties imparted on the metal by the ligand. This dissertation highlights the use of chelating nitrogen-donor ligands with group 4 (Ti and Zr), group 13 (Al), and group 11 (Cu) metals. In Chapter 2, the reactivity of di(3-methylindolyl)methanes and tri(3methylindolyl)methane have been studied with titanium and zirconium. Monocyclopentadienyl complex CpTiL (L= tris(3-methylindolyl)methane), bis(cyclopentadienyl) complexes Cp 2TiL (L= di(3-methylindolyl)-2-pyridylmethane), and Cp2ZrL (L= di(3-methylindolyl)-2-methoxyphenylmethane and di(3-methylindolyl)-2-pyridylmethane) were synthesized in order to probe the coordination of the di- and tri(3-methylindolyl)methane ligands. These ligands present the advantage of being pi-acidic since the lone pairs on the nitrogens are delocalized over the aromatic rings. This is evident from considerable lengthening of Nindolyl-M bonds compared to Namido-M bonds. Also, diethylamido complexes L2Ti(NEt 2)2 (6a and 6b) and L2Zr(THF)(NEt 2)2 (7a and 7b) were prepared (L = phenyldi(3-methylindolyl)methane or 4-bromophenyldi(3-methylindolyl)methane. All complexes have been characterized by NMR spectroscopy (1H, 13C) and select complexes were further characterized by elemental analyses and X ray crystallography. Complexes 6a, 6b 7a, and 7b were tested as precatalysts for ethylene polymerization in the presence of methylaluminuoxane (MAO). Polymerization activities were low.

ISBN: 9780542897740Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper.
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245 1 0 $a Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper.
300 $a 155 p.
500 $a Source: Dissertation Abstracts International, Volume: 67-09, Section: B, page: 5064.
500 $a Advisers: Mark R. Mason; Bruce A. Averill.
502 $a Thesis (Ph.D.)--The University of Toledo, 2006.
520 $a Nitrogen-donor ligands play an important role in inorganic and organometallic chemistry. In general, the ligand design is typically tailored to address specific transformations. In particular, the interplay of electronics and sterics dictates the properties imparted on the metal by the ligand. This dissertation highlights the use of chelating nitrogen-donor ligands with group 4 (Ti and Zr), group 13 (Al), and group 11 (Cu) metals. In Chapter 2, the reactivity of di(3-methylindolyl)methanes and tri(3methylindolyl)methane have been studied with titanium and zirconium. Monocyclopentadienyl complex CpTiL (L= tris(3-methylindolyl)methane), bis(cyclopentadienyl) complexes Cp 2TiL (L= di(3-methylindolyl)-2-pyridylmethane), and Cp2ZrL (L= di(3-methylindolyl)-2-methoxyphenylmethane and di(3-methylindolyl)-2-pyridylmethane) were synthesized in order to probe the coordination of the di- and tri(3-methylindolyl)methane ligands. These ligands present the advantage of being pi-acidic since the lone pairs on the nitrogens are delocalized over the aromatic rings. This is evident from considerable lengthening of Nindolyl-M bonds compared to Namido-M bonds. Also, diethylamido complexes L2Ti(NEt 2)2 (6a and 6b) and L2Zr(THF)(NEt 2)2 (7a and 7b) were prepared (L = phenyldi(3-methylindolyl)methane or 4-bromophenyldi(3-methylindolyl)methane. All complexes have been characterized by NMR spectroscopy (1H, 13C) and select complexes were further characterized by elemental analyses and X ray crystallography. Complexes 6a, 6b 7a, and 7b were tested as precatalysts for ethylene polymerization in the presence of methylaluminuoxane (MAO). Polymerization activities were low.
520 $a In Chapter 3, alkyl complexes (2a-5) of aluminum LAIR (L = di(3-methylindolyl)-2-pyridylmethane, R = Me, Et, iBu, tBu) were prepared and characterized. Also, a dialuminum complex was obtained upon reaction of the ligand with 2 equivalents of AlMe3. Complexes 2a-5 were utilized in an attempt to generate a cationic complex that can bind carbon monoxide. Reactions with trityl salts or etherate acids were inconclusive in terms of generating a stable cationic aluminum complex.
520 $a In Chapter 4, acetonitrile complexes [LCu(NCCH3)][PFD] were synthesized using tris(2-pyridyl)carbinol and tris(1-pyrazolyl)methane) ( 8 and 9). These complexes were tested for alkene binding with select terminal and internal alkenes. Equilibrium constants were calculated by means of NMR spectroscopy. The effects of ligand sterics and electronics were also investigated.
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