Conversion between Doubly and Triply Carboxylate Bridged Bis(ethylzinc) Complexes and Formation of the (μ-Oxo)tetrazinc Carboxylate [Zn[subscript 4]O(Ar[superscript Tol]CO[subscript 2)[subscript 6]]
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Author(s) •
Lippard, Stephen J.
Minier, Mikael Antoine
Date Issued
March 2014
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
Minier, Mikael A., and Stephen J. Lippard. “Conversion between Doubly and Triply Carboxylate Bridged Bis(ethylzinc) Complexes and Formation of the (μ-Oxo)tetrazinc Carboxylate [Zn[subscript 4]O(Ar[superscript Tol]CO[subscript 2)[subscript 6]].” Organometallics 33, no. 6 (March 24, 2014): 1462–1466.
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Author's final manuscript
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 [Zn[subscript 2](Ar[superscript Tol]CO[subscript 2])[subscript 2](Et)[subscript 2](THF)[subscript 2]] (1), [Zn[subscript 2](Ar[superscript Tol]CO[subscript 2])[subscript 3](Et)(THF)] (2), and diethylzinc (Ar[superscript Tol] = 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 [Zn[subscript 4]O(Ar[superscript Tol]CO[subscript 2])[subscript 6]] (3).
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/om5000503