An Air- and Water-Tolerant Zinc Hydride Cluster That Reacts Selectively With CO2

David M Ermert; Ion Ghiviriga; Vincent J Catalano; Jason Shearer; Leslie J Murray

doi:10.1002/anie.201501539

An Air- and Water-Tolerant Zinc Hydride Cluster That Reacts Selectively With CO2

Angew Chem Int Ed Engl. 2015 Jun 8;54(24):7047-50. doi: 10.1002/anie.201501539. Epub 2015 Apr 27.

Authors

David M Ermert¹, Ion Ghiviriga², Vincent J Catalano³, Jason Shearer³, Leslie J Murray⁴

Affiliations

¹ Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA).
² Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA).
³ Department of Chemistry, University of Nevada, Reno, NV 89557 (USA).
⁴ Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA). murray@chem.ufl.edu.

PMID: 25914385
DOI: 10.1002/anie.201501539

Abstract

The reaction of [Zn3Cl3L], in which L(3-) is a tris(β-diketiminate) cyclophane, with K(sBu)3BH afforded [Zn3(μ-H)3L] (2), as confirmed by NMR spectroscopy, NOESY, and X-ray crystallography. The complex 2 was air-stable and unreactive towards water, methanol, and other substrates (e.g., nitriles) at room temperature over 24 h but reacted with CO2 (ca. 1 atm) to generate [Zn3(μ-H)2(μ-1,1-O2CH)] (3). In contrast, [Zn3(OH)3L] (4) was found to be unreactive toward CO2 over the course of several days at 90 °C.

Keywords: carbon dioxide; cyclophanes; diketiminates; reduction; zinc hydrides.