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Tris(pyrazolyl)borate Copper Hydroxide Complexes Featuring Tunable Intramolecular H-bonding

preprint
submitted on 22.03.2019 and posted on 22.03.2019 by Evan Gardner, Caitlyn Cobb, Jeffery A. Bertke, Timothy H. Warren
A modular synthesis provides access to a series of new tris(pyrazolyl)borate ligands XpyMeTpK that possess a single functionalized pendant pyridyl (py) or pyrimidyl (pyd) arm designed to engage in tunable intramolecular H-bonding to metal–bound functionalities. To illustrate such H-bonding interactions, a series of [XpyMeTpCu]2(𝜇–OH)2(6a–6e) complexes were synthesized from the corresponding XpyMeTpCu–OAc (5a–5e) complexes. Single crystal X-ray structures of three new dinuclear [XpyMeTpCu]2(𝜇–OH)2complexes reveal H-bonding between the pendant heterocycle and bridging hydroxide ligands while the donor arm engages the copper center in an unusual monomeric DMAPMeTpCu–OH complex. Vibrational studies (IR) of each bridging hydroxide complex reveal reduced 𝜈OH frequencies that tracks with the H-bond accepting ability of the pendant arm.

Funding

Department of Energy Basic Energy Sciences DE-SC001779

History

Email Address of Submitting Author

thw@georgetown.edu

Institution

Georgetown University, Department of Chemistry

Country

USA

ORCID For Submitting Author

0000-0001-9217-8890

Declaration of Conflict of Interest

No COI

Exports