Asymmetric dinuclear copper(I) complexes of bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine with short copper-copper distances |
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Authors: | Goodwin Jocelyn M Chiang Pin-Chieh Brynda Marcin Penkina Katerina Olmstead Marilyn M Patten Timothy E |
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Affiliation: | Department of Chemistry, University of California at Davis, One Shields Avenue, Davis, CA 95616-5295, USA. |
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Abstract: | Addition of two equivalents of CuCl to deprotonated bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine (PETAEA) and its derivatives yielded new types of dinuclear Cu(I) complexes, Cu(mu-PETAEA)CuCl, Cu(mu-PEMAEA)CuCl, and Cu(mu-PENAEA)CuCl (PEMAEA is the 4-methoxyphenyl derivative of PETAEA and PENAEA is the 4-nitrophenyl derivative), exhibiting a four coordinate N(4)Cu center, a two coordinate NCuCl center, and a metal-metal distance within the range of 2.6572(8) to 2.6903(3) A. Analysis of the covalent radii for four coordinate and two coordinate copper(I), the acute copper-nitrogen-copper angles, and density functional theory (DFT) calculations suggest a weak attraction between the two copper atoms. The complexes apparently formed in a two-step process with the formation of the tetracoordinate mononuclear complex preceding the coordination of a second equivalent of CuCl to the lone pair of the sulfonamidate ligand. |
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