Synthesis and Reactivity of Titanium and Zirconium Complexes Supported by a Multidentate Monoanionic [N2P2] Ligand

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• 作者：Wayne A. Chomitz ; Andrew D. Sutton ; Jamin L. Krinsky ; John Arnold
• 刊名：Organometallics
• 出版年：2009
• 出版时间：June 22, 2009
• 年：2009
• 卷：28
• 期：12
• 页码：3338-3349
• 全文大小：291K
• 年卷期：v.28,no.12(June 22, 2009)
• ISSN：1520-6041

文摘

The coordination chemistry of titanium and zirconium complexes supported by the monoanionic multidentate ligand [N₂P₂] (where [N₂P₂] = ^tBuN⁻SiMe₂N(CH₂CH₂PⁱPr₂)₂) is presented. The zirconium(IV) halide complex [N₂P₂]ZrCl₃ (1) serves as a precursor to the alkyl species [N₂P₂]Zr(CH₂SiMe₃)₃ (2) and [N₂P₂]ZrMe₃ (3). The coordination behavior of the [N₂P₂] ligand in compound 3 is determined using NMR and X-ray diffraction data, and protonation of 3 results in the formation of the cationic species {[N₂P₂]ZrMe₂}{B(C₆H₅)₄} (4). The reduction of 1 in the presence of various traps leads to the isolation of ([N₂P₂]ZrCl)₂(μ-η²:η²-N₂) (5), ([N₂P₂]ZrCl)₂(μ-Cl)₂ (6), and [N₂P₂]ZrAr* (9). The titanium(III) halide complex [N₂P₂]TiCl₂ (10) also serves as a precursor to alkyl and reduced species [N₂P₂]TiMe₂ (11) and ([N₂P₂]TiCl)₂(μ-N₂) (12). Alkylation of 12 results in the formation of ([N₂P₂]TiCH₂SiMe₃)₂(μ-N₂) (13), and the degree of reduction of the N₂ moiety in 12 and 13 is examined using X-ray crystallography and Raman spectroscopy. A series of titanium(IV) imido complexes [N₂P₂]TiCl(N^tBu) (14), [N₂P₂]TiMe(N^tBu) (15), and {[N₂P₂]Ti(N^tBu)}{MeB(C₆F₅)₃)} (16) are synthesized, and the coordination behavior of the [N₂P₂] ligand is presented.