Synthesis, structure and dioxygen reactivity of a bis(µ-iodo)dicopper(I) complex supported by the [N-(3,5-di-tert-butyl-2-hydroxybenzyl)-N,N-di-(2-pyridylmethyl)]amine ligand
Abstract
The air-sensitive bis(µ-iodo)dicopper(I) complex 1 supported by [N-(3,5-di-tert-butyl-2-hydroxybenzyl)-N,N-di-(2-pyridylmethyl)]amine (L) has been prepared by treating copper(I) iodide with L in anhydrous THF. Compound 1 crystallizes as a dimer in space group C2/c. Each copper(I) center has distorted tetrahedral N2I2 coordination geometry with Cu–N(pyridyl) distances 2.061(3) and 2.063(3) Å, Cu–I distances 2.6162(5) and 2.7817(5) and a CuCu distance of 2.9086(8) Å. Complex 1 is rapidly oxidized by dioxygen in CH2Cl2 with a 1 : 1 stoichiometry giving the bis(µ-iodo)peroxodicopper(II) complex [Cu(L)(µ-I)]2O2 (2). The reaction of 1 with dioxygen has been characterized by UV-vis, mass spectrometry, EPR and Cu K-edge X-ray absorption spectroscopy at low temperature (193 K) and above. The mass spectrometry and low temperature EPR measurements suggested an equilibrium between the bis(µ-iodo)peroxodicopper(II) complex 2 and its dimer, namely, the tetranuclear (peroxodicopper(II))2 complex [Cu(L)(µ-I)]4O4 (2). Complex 2 undergoes an effective oxo-transfer reaction converting PPh3 into OPPh3 under anaerobic conditions. At sufficiently high concentration of PPh3, the oxygen atom transfer from 2 to PPh3 was followed by the formation of [Cu(PPh3)3I]. The dioxygen reactivity of 1 was compared with that known for other halo(amine)copper(I) dimers.
Additional Information
© The Royal Society of Chemistry 2006 Received 30th September 2005, Accepted 25th January 2006. First published on the web 14th February 2006. This work was supported by Academia Sinica and by grants from the National Science Council (NSC 90-2113-M-001-006, 90-2113-M-001-080 and 91-2113-M-006-006). The part of the work done in Hong Kong was supported by a Direct Grant (A/C 2060271) of The Chinese University of Hong Kong. We are grateful to Dr Jyh-Fu Lee of the Research Division of the National Synchrotron Radiation Research Center (NSRRC), Hsinchu, Taiwan for his kind assistance in the X-ray absorption measurements. Miss H.-W. Li and Professor Thomas C. W. Mak of CUHK solved the X-ray structure of [CuL(µ-I)]2·2CH2Cl2, and Mr Yuh-Sheng Wen solved the X-ray structure of [Cu(L)Cl]Cl·2CHCl3. We are indebted to these colleagues for their contributions to the work. Finally, one of us (H.K.L.) would like to thank Dr Yee-Lok Wong for helpful discussions on the synthesis of 1; and S.V.P. and S.I.C. are grateful to Dr Peter P.-Y. Chen for discussions on the interpretation of the EPR results. Single crystals of the solvated complex 1·2CH2Cl2 were obtained from a dichloromethane solution. Crystals suitable for crystallographic studies were mounted in Lindemann glass capillaries and sealed under nitrogen. Data were collected using graphite-monochromatized Mo-K radiation ( = 0.71073 Å) on a Bruker SMART CCD diffractometer at 293 K using frames of oscillation range 0.3°, with 2.19° < < 28.02°. Diffraction measurements for a single crystal of 4·2CHCl3 were carried out with a Bruker-Nonius Apex CCD diffractometer at 100 K using graphite-monochromatized Mo-K radiation ( = 0.71073 Å) and frame of oscillation range 0.5°, with 2.30° < < 27.48°. An empirical absorption correction was applied using the SADABS program.30 The crystal structures were solved by the direct methods and refined by full-matrix least squares on F2 using the SHELXTL program package.31 CCDC reference numbers 285531 and 286337. For crystallographic data in CIF or other electronic format see DOI: 10.1039/b513898aAttached Files
Published - PAVdt06.pdf
Supplemental Material - PAVdt06cryst.txt
Supplemental Material - PAVdt06supp.pdf
Cover Image - PAVdt06diag.gif
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Additional details
- Eprint ID
- 7092
- Resolver ID
- CaltechAUTHORS:PAVdt06
- Academia Sinica
- NSC 90-2113-M-001-006
- National Science Council (Taipei)
- NSC 90-2113-M-001-080
- National Science Council (Taipei)
- NSC 91-2113-M-006-006
- National Science Council (Taipei)
- A/C 2060271
- Chinese University of Hong Kong
- Created
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2007-01-08Created from EPrint's datestamp field
- Updated
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2021-11-08Created from EPrint's last_modified field