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Conversion Between Doubly and Triply Carboxylate-Bridged Di(ethylzinc) Complexes and Formation of the (μ-Oxo)tetrazinc Carboxylate [Zn4O(ArTolCO2)6].


ABSTRACT: Ethylzinc 2,6-bis(p-tolyl)benzoate converts between two forms in solution. Through NMR spectroscopic techniques and X-ray crystallography, the species in equilibrium were identified as [Zn2(ArTolCO2)2(Et)2(THF)2] (1), [Zn2(ArTolCO2)3(Et)(THF)] (2), and diethyl zinc (ArTol = 2,6-bis(p-tolyl)phenyl). The equilibrium provides a model for understanding the speciation between doubly and triply m-terphenylcarboxylate-bridged diiron(II) and mononuclear iron(II) complexes. Evidence is presented for the occurrence of coordinatively unsaturated trigonal zinc species in solution. Both 1 and 2 decompose in air to form the T-symmetric oxozinc carboxylate, [Zn4O(ArTolCO2)6] (3).

SUBMITTER: Minier MA 

PROVIDER: S-EPMC3994167 | biostudies-literature | 2014 Mar

REPOSITORIES: biostudies-literature

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Conversion Between Doubly and Triply Carboxylate-Bridged Di(ethylzinc) Complexes and Formation of the (μ-Oxo)tetrazinc Carboxylate [Zn<sub>4</sub>O(Ar<sup>Tol</sup>CO<sub>2</sub>)<sub>6</sub>].

Minier Mikael A MA   Lippard Stephen J SJ  

Organometallics 20140301 6


Ethylzinc 2,6-bis(<i>p</i>-tolyl)benzoate converts between two forms in solution. Through NMR spectroscopic techniques and X-ray crystallography, the species in equilibrium were identified as [Zn<sub>2</sub>(Ar<sup>Tol</sup>CO<sub>2</sub>)<sub>2</sub>(Et)<sub>2</sub>(THF)<sub>2</sub>] (<b>1</b>), [Zn<sub>2</sub>(Ar<sup>Tol</sup>CO<sub>2</sub>)<sub>3</sub>(Et)(THF)] (<b>2</b>), and diethyl zinc (Ar<sup>Tol</sup> = 2,6-bis(<i>p</i>-tolyl)phenyl). The equilibrium provides a model for understanding  ...[more]

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