Document Type

Article

Publication Date

7-3-2018

Publication Title

Inorganic Chemistry

Volume

57

Issue

14

Pages

8307-8316

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 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.

COinS