Homo- and Heterometallic Complexes of Tetra-(Di-Substituted Hydroxybenzyl)-N,N′-Ethylenediamine Derivatives

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• 作者：Timothy J. Boyle ; Harry D. Pratt ; III ; Leigh Anna M. Ottley ; Todd M. Alam ; Sarah K. McIntyre ; Mark A. Rodriguez ; Joshua Farrell ; Charles F. Campana
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：October 5, 2009
• 年：2009
• 卷：48
• 期：19
• 页码：9191-9204
• 全文大小：1167K
• 年卷期：v.48,no.19(October 5, 2009)
• ISSN：1520-510X

文摘

The coordination behavior of a series of group 4 metal alkoxides [M(OR)₄] modified by a set of novel substituted hydroxybenzyl ethylene diamine (H₄-ED-L₄) ligands {[tetra(3,5-di-t-butyl-2-hydroxybenzyl)-N,N′-ethylenediamine] termed H₄-ED-DBP₄ (1), [tetra(3,5-di-t-amyl-2-hydroxybenzyl)-N,N′-ethylenediamine] termed H₄-ED-DAP₄ (1a), and [tetra(3,5-dichloro-2-hydroxybenzyl)-N,N′-ethylenediamine] termed H₄-ED-DCP₄ (2)} was elucidated. The reaction of 1 or 1a with the M(OR)₄ precursor led to the isolation of the structural similar species M(ED-L₄) where L = DBP, M = Ti (3), Zr (4), Hf (5); L = DAP, M = Zr (4a), Hf (5a). In contrast, the reaction of 2 with the M(OR)₄ precursors yielded Ti(ED-DCP₄) (6), (py)₂Zr(ED-DCP₄) (7), and (HOBu^t)Hf(ED-DCP₄) (8) where py = pyridine and HOBu^t = HOC(CH₃)₃. For 3−6, the cations of the monomeric species were completely encapsulated by all available heteroatoms (four O and two N) of the ED-L₄ ligands, yielding an octahedral geometry for each metal center. For 7 and 8, an identical binding by the ED-DCP₄ ligand was observed with the additional coordination of Lewis basic adducts, forming 8- and 7-coordinated metal centers, respectively. Switching to +2 cations led to the isolation of [(THF)Ca]₂(ED-DBP₄) (9a) where THF = tetrahydrofuran, {[(py)Ca]₄(ED-(μ-DBP-η⁶)₄)₂}_n (9b), and [(py)Zn](ED-DBP₄)[Zn(py)₂] (10) •5py and [(py)Sn]₂(ED-DBP₄) (11). The structures of these species were significantly different in arrangement compared to the Group 4 derivatives. Further attempts to produce a mixed +4/+2 cationic species yielded [(py)(ONep)₂Ti(ED-DBP₄)Zn(py)] (12). Reacting the single-source precursor Co[μ-OC₆H₄(CHMe₂)₂-2)₂Li(py)₂]₂ with 1, led to the isolation of (py)Li[ED-DBP₃(H-DBP)]Co (13), with one of the phenol protons remaining unreacted. The synthesis and characterization of these compounds are presented in detail.