Journal article
Coordination Chemistry of N,N,N ',N '-Tetrakis(3,5-substituted benzyl-2-oxide)-2,2 '-(ethylenedioxy)diethanamine Modified Group 4 Metal Alkoxides
Inorganic chemistry, v 51(21), pp 12023-12031
05 Nov 2012
PMID: 23088334
Abstract
The coordination behavior of a set of (ethylenedioxy)diethanamine-based tetraphenol ligands with a series of Group 4 metal alkoxides ([M(OR)(4)]) was determined. The ligands were synthesized from a modified Mannich reaction and fully characterized as N,N,N',N' -tetrakis (3,5 - tert-butyl-b e nzyl- 2 -hydroxy) -2,2'- (ethylenedioxy) diethanamine, termed H-4-OEA-DBP4 (1), and N,N,N',N'-tetrakis(3,5-chloro-benzyl-2-hydroxy)-2,2'-(ethylenedioxy)diethanamine, termed H-4-OEA-DCP4 (2): The reaction of 1 with a set of [M(OR)4] [M = Ti, Zr, or Hf; OR = iso-propcodde (OH), neo-pentoxide (ONep), or tertbutoxide (OBut)] precursors led to the isolation of ROPri)2Tik(mu-OEA-DBP4) (3), RONep)(2)Ti](2)(mu-OEA-DBP4) (4), and [(OBui)(2)M](2)(mu-OEA-DBP4) where M = Ti (5), Zr (6), or Hf (7). In addition, the [(ONep)(2)Ti](2)(mu-OEA-DCP4) (4a) derivative was isolated from the reaction of 2 and [Ti(ONep)(4)], demonstrating the similarity of coordination behavior between the two OEA-R-4 ligands. For 3-7, the metal center adopts a slightly distorted octahedral geometry by binding the two O atoms of the phenoxide moiety, as well as one N and one O atom from the OEA moieties, while retaining two of the original OR ligands. Solution NMR demonstrates inequivalent protons for the majority of the bound OEA ligands, which argues for retention of structure in solution. The synthesis and characterization of these compounds are presented in detail.
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Details
- Title
- Coordination Chemistry of N,N,N ',N '-Tetrakis(3,5-substituted benzyl-2-oxide)-2,2 '-(ethylenedioxy)diethanamine Modified Group 4 Metal Alkoxides
- Creators
- Timothy J. Boyle - Sandia National LaboratoriesDaniel T. Yonemoto - Sandia National LaboratoriesLeigh Anna Steele - Sandia National LaboratoriesJoshua Farrell - College of the Holy CrossPeter Renehan - College of the Holy CrossTaylor Huhta - College of the Holy Cross
- Publication Details
- Inorganic chemistry, v 51(21), pp 12023-12031
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 9
- Grant note
- National Institute for Nano-Engineering (NINE) CHE04-43580 / National Science Foundation CRIF:MU award DE-AC04-94AL85000 / U.S. Department of Energy's National Nuclear Security Administration; National Nuclear Security Administration Laboratory Directed Research and Development (LDRD) programs at Sandia National Laboratories
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- School of Biomedical Engineering, Science, and Health Systems; Drexel University
- Web of Science ID
- WOS:000313220200093
- Scopus ID
- 2-s2.0-84868369259
- Other Identifier
- 991019356497604721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear