Structural and spectroscopic studies of some copper(I) halide tert-butyl isocyanide adducts

Bowmaker, Graham A. and Hanna, John V. and Hahn, F. Ekkehardt and Lipton, Andrew S. and Oldham, Carolyn E. and Skelton, Brian W. and Smith, Mark E. and White, Allan H. (2008) Structural and spectroscopic studies of some copper(I) halide tert-butyl isocyanide adducts. Dalton Transactions, 2008 (13). pp. 1710-1720. ISSN 1477-9226

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Abstract

Single-crystal structural characterizations confirm the existence of the unusual 1 : 4 copper(I) halide : unidentate ligand adducts [Cu(CNt-Bu)4]X for X = Cl, Br (two forms), I (the chloride and one form of the bromide being solvated) with crystal packing dominated by stacks of interleaving cations. Cu–C range between 1.941(2) and 1.972(4) Å. The structure of the 1 : 2 chloride complex is also recorded, being [ClCu(CNt-Bu)2], with the copper(I) atom environment trigonal planar, while CuCN : (CNt-Bu) (1 : 1) is a single-stranded polymer which spirals about a crystallographic 3-axis (CN scrambled), the ligands being pendant from the …CuCNCuCN… string. The 65Cu static broadline NMR spectra of [Cu(CNt-Bu)4]I and [Cu(CNt-Bu)4]Br·H2O in the solid state exhibit dominant, narrow −1/2 ↔ +1/2 central transition resonances and associated ±1/2 ↔ ±3/2 satellite transition resonances which are characteristic of first-order quadrupole broadened systems, while associated high-resolution 65Cu MAS NMR data provide accurate measurement of the 65Cu isotropic chemical shifts. Both approaches provide complete data on the quadrupole and chemical shift interactions which contribute to these spectra. Far-IR spectra of products of reactions involving a range of CuX : t-BuNC ratios reveal the existence of 1 : 1.5 adducts for X = Br, I. Metal–carbon and metal-halogen bands are assigned in the far-IR spectra, which indicate a binuclear double halogen-bridged structure for the 1 : 1.5 complexes.

Item Type:
Journal Article
Journal or Publication Title:
Dalton Transactions
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1600/1604
Subjects:
?? INORGANIC CHEMISTRY ??
Departments:
ID Code:
65122
Deposited By:
Deposited On:
07 Jun 2013 13:59
Refereed?:
Yes
Published?:
Published
Last Modified:
19 Sep 2023 01:06