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Issue 14, 2001
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The effects of distal ligand substitution on the copper(II)/bis-(2,6-dipyrazol-1-ylpyridine) centre

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Abstract

The complex [Cu(L4)2](BF4)2 (3; L4 = 2-[pyrazol-1-yl]-6-[3-{2,4,6-trimethylphenyl}pyrazol-1-yl]pyridine) has been synthesised. Complex 3 crystallises in two crystal forms from MeNO2/Et2O. The monoclinic α-form contains crystallographically ordered, pseudo-Jahn–Teller elongated {dy2 − z2}1 Cu(II) ions that are structurally very similar to [Cu(L2)2](BF4)2 (1; L2 = 2,6-dipyrazol-1-ylpyridine). The Cu ion in the orthorhombic β-polymorph at 180 K exhibits Cu–N bond lengths that are rather different from the α-form, and which could correspond to a disordered {dy2 − z2}1 Cu(II) centre; or, to a static, rhombically compressed ion with a {dz2}1 ground state. Variable temperature EPR data favour the former interpretation. A crystal structure at 31 K of [Cu(L3)2](BF4)2 (2; L3 = 2,6-bis-[3-{2,4,6-trimethylphenyl}pyrazol-1-yl]pyridine), a genuine {dz2}1 ion, is also described. Comparison of the crystallographic data of 13 shows that the {dy2 − z2}1-to-{dz2}1 ground state change occurs concomitantly with only a small z-axis compression.

Graphical abstract: The effects of distal ligand substitution on the copper(II)/bis-(2,6-dipyrazol-1-ylpyridine) centre

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Article information


Submitted
06 Apr 2001
Accepted
30 May 2001
First published
03 Jul 2001

J. Chem. Soc., Dalton Trans., 2001, 2083-2088
Article type
Paper

The effects of distal ligand substitution on the copper(II)/bis-(2,6-dipyrazol-1-ylpyridine) centre

N. K. Solanki, M. A. Leech, E. J. L. McInnes, J. P. Zhao, F. E. Mabbs, N. Feeder, J. A. K. Howard, J. E. Davies, J. M. Rawson and M. A. Halcrow, J. Chem. Soc., Dalton Trans., 2001, 2083
DOI: 10.1039/B103142M

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