Copper(II) environments in some macrobicycle complexes at room and low temperatures: Some novel binuclear chloro-bridged systems

Engelhardt, Lutz M., Grondahl, Lisbeth, Harrowfield, Jack M., Ralph, Stephen F., Sargeson, Alan M., Skelton, Brian W., Sobolev, Alexandre N. and White, Allan H. (2011) Copper(II) environments in some macrobicycle complexes at room and low temperatures: Some novel binuclear chloro-bridged systems. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 71 3-4: 353-362. doi:10.1007/s10847-011-9952-3


Author Engelhardt, Lutz M.
Grondahl, Lisbeth
Harrowfield, Jack M.
Ralph, Stephen F.
Sargeson, Alan M.
Skelton, Brian W.
Sobolev, Alexandre N.
White, Allan H.
Title Copper(II) environments in some macrobicycle complexes at room and low temperatures: Some novel binuclear chloro-bridged systems
Journal name Journal of Inclusion Phenomena and Macrocyclic Chemistry   Check publisher's open access policy
ISSN 1573-1111
1388-3127
Publication date 2011-12-01
Year available 2011
Sub-type Article (original research)
DOI 10.1007/s10847-011-9952-3
Volume 71
Issue 3-4
Start page 353
End page 362
Total pages 10
Editor John D. Lamb
Place of publication Dordrecht, Netherlands
Publisher Springer
Collection year 2012
Language eng
Formatted abstract
Single crystal X-ray studies are recorded for five copper(II) complexes of macrobicyclic ligands. In both [Cu(sar)][ZnCl4] (295, 170 K) determinations (‘sar’ = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) and [Cu(NH3)2sar]Cl4·6H2O (295 K), the ligand encapsulates the copper atom by coordinating through all six nitrogen atoms, though distortions of the primary coordination sphere from an octahedral array are both marked and quite different in the two cases. [Cu(sar)]2+ undergoes a relatively facile detachment of one ligand strand in acid solution, giving a species with a different bound-N configuration to that of the reactant and which may be crystallised in various forms. In the solid of composition Cu(ClO4)2·2HClO4·½HCl·H2O·sar (295 K) the complex present is binuclear ‘[(sarH)CuClCu(sarH2)](ClO4)2H2O’, with the linear CuClCu array comprising the apical bonds of a pair of square-pyramidal ClCuN4 components. In mononuclear [Cu(sarH2)(ONO2)](NO3)3·3H2O (295 K) two of the ligand strings coordinate in a quasi-square-planar array, with an approach of an anionic oxygen atom to one of the remaining opposed axial coordination sites. In the crystalline complex formed between copper(II) triflate (Cu(tfs)2; ‘tfs’ = F3CSO3−) and the expanded macrobicycle Me5tricosaneN6 (Me5tricosaneN6fac-1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosane), the ligand, despite the lack of any protonation, is found (295, 150 K) to be bound in a quinquedentate form, with one triflate-O occupying the sixth coordination site about the metal, in the mononuclear complex [Cu(Me5tricosaneN6)(O-tfs)](tfs). This contrasts with the perchlorate counterpart wherein all nitrogen atoms are coordinated within an encapsulating cage.
Keyword Copper(II)
Cage ligands
Sarcophagine
Crystal structure
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes From the issue entitled "Special issue to commemorate the 75th birthday of Prof.Leonard F.Lindoy"

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 16 Dec 2011, 19:51:59 EST by Lucy O'Brien on behalf of School of Chemistry & Molecular Biosciences