Synthesis and Characterization of Cross-Bridged Cyclams and Pendant-Armed Derivatives and Structural Studies of Their Copper(II) Complexes

Edward H. Wong,* Gary R. Weisman,* Daniel C. Hill, David P. Reed, Mark E. Rogers, Jeffrey S. Condon, Maureen A. Fagan, Joseph C. Calabrese, Kin-Chung Lam,§ Ilia A. Guzei,§# and Arnold L. Rheingold§
Contribution from the Department of Chemistry, University of New Hampshire, Durham, New Hampshire 03824-3598, the Central Research and Development Department, E. I. DuPont Nemours & Co., Inc., Experimental Station, Wilmington, Delaware 19880-0228, and the Crystallography Laboratory, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716
J. Am. Chem. Soc., 2000, 122 (43), pp 10561–10572
DOI: 10.1021/ja001295j
Publication Date (Web): October 18, 2000
Copyright © 2000 American Chemical Society

Abstract

A series of 1,4,8,11-tetraazabicyclo[6.6.2]hexadecane ligands, including the parent compound, N,N‘-dialkyl variants, and the first N,N‘-di-pendant-arm derivatives have been synthesized by a short, efficient, and conceptually novel approach. Their copper(II) complexes have been prepared, and four of these were structurally characterized by X-ray diffraction. In all four complexes, the cross-bridged tetraamine ligand was found to be cis-folded, coordinating the metal cation within its molecular cleft using all four nitrogen lone pairs. Geometries intermediate between idealized square pyramidal and trigonal bipyramidal coordination were found for three of the complexes, whereas a distorted octahedral copper coordination was found for the complex of a di-pendant-arm cross-bridged cyclam.

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History

  • Published In Issue November 01, 2000
  • Received April 13, 2000

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