ISSN:
1434-1948
Keywords:
Macrocycles
;
Nickel
;
Redox chemistry
;
Schiff bases
;
S ligands
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A single crystal X-ray analysis of [Ni2L1](ClO4)2· MeCN · 1/4 H2O, 1a [formed directly from a mixture of nickel(II) template ions, 2,6-diformyl-4-methyl-thiophenolate, and 1,4-diaminobutane] reveals that the nickel(II) ions are in square-planar N2S2 environments and that the four “bowed” dinickel macrocycles in the asymmetric unit pack around a single central perchlorate template ion encapsulating it to form “star” clusters of stoichiometry {[Ni2L1]4(ClO4)}7+. These “stars” stack together, via π-π-stacking interactions, to form two-dimensional sheets, which are separated from one another by layers of the remaining perchlorate anions and solvent molecules. Reduction, by NaBH4, of the four imine bonds in [Ni2L2](ClO4)22a (analogous to 1a but formed from 1,3-diaminopropane not 1,4-diaminobutane) or [Ni2L2](CF3SO3)22b to amine bonds produces the corresponding tetra-amine complex, [Ni2L3](ClO4)23. These complexes are shown to contain diamagnetic nickel(II) ions by a combination of magnetic, NMR and UV/Vis spectroscopic results. The 1H NMR spectra of 1-3 run in [D3]MeNO2 and in [D3]MeCN are consistent with increasing axial binding ability in the order: 3 〈 2 〈 1. Thiocyanate ion binding studies reveal that 1 and 2 are able to coordinate two thiocyanate ions, forming [Ni2L1(NCS)2] 4 and [Ni2L2(NCS)2] 5 respectively, whereas 3 does not. Single crystal X-ray analyses of complexes 4· 2 MeCN and 5· MeCN show that adjacent square-planar and octahedral nickel(II) ions result. Two one-electron oxidations and two one-electron reductions are a feature of the electrochemistry of 1-3 in MeCN: curiously, the potentials for the oxidation processes are almost invariant whereas those for the reduction processes vary as anticipated. EPR spectroscopy shows that the first one-electron reduction process and the first one-electron oxidation process are metal centred. Spectroelectrochemical studies and redox titrations indicate that a purplish-coloured complex is produced by one-electron oxidation of 2 (λ = 870 nm, ε = 1320 L mol cm-1). The synthesis of a phenolate analogue, [Ni2L′(MeCN)4](ClO4)2 (6), of the thiophenolate complex 2a is also detailed. Complex 6 undergoes two one-electron oxidations in MeCN, but, in contrast to the thiophenolate complexes 1-3, these occur at much higher potentials. Only a single one-electron reduction process is observed and this occurs at a more negative potential than for any of 1-3.
Additional Material:
11 Ill.
Type of Medium:
Electronic Resource
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