Document Type

Article

Publication Date

7-3-2018

Publication Title

Inorganic Chemistry

Volume

57

Issue

14

Pages

8307-8316

Publisher Name

American Chemical Society

Abstract

A series of four- and five-coordinate Ni(II) complexes CztBu(PyriPr)2NiX (13 and 1·THF–3·THF), where X = Cl, Br, and I, were synthesized and fully characterized by NMR and UV–vis spectroscopy, X-ray crystallography, cyclic voltammetry, and density functional theory calculations. The solid-state structures of 13 reveal rare examples of seesaw Ni(II) complexes. In solution, 13 bind reversibly to a THF molecule to form five-coordinate adducts. The electronic transitions in the visible region (630–680 nm), attributed to LMCT bands, for 13 exhibit a bathochromic shift. The thermochromic tendency of the five-coordinate complexes implies the loss of THF coordination at elevated temperatures. Finally, the electronic properties of all Ni(II) complexes were studied by time-dependent density functional theory calculations to characterize the nature of the excited states.

Comments

Author Posting. © American Chemical Society 2018. This is the author's version of the work. This article is posted here by permission of the ACS for personal use, not for redistribution. The article was published in Inorganic Chemistry, 2018, https://doi.org/10.1021/acs.inorgchem.8b00958.

Creative Commons License

Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 License.

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