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Author Fneich, Bassam N
Title Chelating nitrogen-donor complexes of titanium, zirconium, aluminum, and copper
book jacket
Descript 155 p
Note Source: Dissertation Abstracts International, Volume: 67-09, Section: B, page: 5064
Advisers: Mark R. Mason; Bruce A. Averill
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
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
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
School code: 0232
Host Item Dissertation Abstracts International 67-09B
Subject Chemistry, Inorganic
Alt Author The University of Toledo
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