T. Boyle, J. Rimsza, J. Farrell
May 2, 2020
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Journal
Journal of Coordination Chemistry
Abstract
Abstract The coordination behavior of the tridentate alkoxy ligand 6,6'-(((2-hydroxyethyl)azanediyl)bis(methylene)) bis(2,4-di-tert-butylphenol) (termed H3-AM-DBP2) with group 4 metal alkoxides ([M(OR)4]) in a 1:1 ratio was previously found to generate [(ONep)Ti(κ 4 (O,O’,O”,N)-AM-DBP2)] and [(OR)Zr(κ 4 (μ-O,O’,O”,N)-AM-DBP2)]2 (M = Zr, Hf). Additional studies revealed that increasing the stoichiometric ratio to 1:2 H3-AM-DBP2:[M(OR)4] led to the isolation of [(ONep)Ti(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-ONep)Ti(ONep)3] (1)•tol, [(OBu t)Zr(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-OBu t )Zr(OBu t )3] (2) and [(OBu t )Hf(κ 4 (μ-O,O’,O”,N)-AM-DBP2)(μ-OBu t)Hf(OBu t )3] (3). The asymmetric dinuclear complexes of 1-3 resemble the chelation of a [M(OR)4] moiety to a “(OR)M(κ 4 (O,O’,O”,N)-AM-DBP2)” fragment. The metal complexed by the AM-DBP2 ligand has a pseudo octahedral geometry while the other metal adopts an intermediate trigonal bipyramidal (TBP-5)/square base pyramidal (SBP-5) geometry for 1 but a distorted SBP-5 for both 2 and 3. The structure and properties of 1-3 were analyzed by computational modeling and fully characterized by standard analytical methods. Graphical Abstract