Redox non-innocence of thioether crowns: spectroelectrochemistry and electronic structure of formal nickel(III) complexes of aza-thioether macrocycles.

The Ni(II) complexes [Ni([9]aneNS(2)-CH(3))(2)](2+) ([9]aneNS(2)-CH(3)=N-methyl-1-aza-4,7-dithiacyclononane), [Ni(bis[9]aneNS(2)-C(2)H(4))](2+) (bis[9]aneNS(2)-C(2)H(4)=1,2-bis-(1-aza-4,7-dithiacyclononylethane) and [Ni([9]aneS(3))(2)](2+) ([9]aneS(3)=1,4,7-trithiacyclononane) have been prepared and can be electrochemically and chemically oxidized to give the formal Ni(III) products, which have been characterized by X-ray crystallography, UV/Vis and multi-frequency EPR spectroscopy. The single-crystal X-ray structure of [Ni(III)([9]aneNS(2)-CH(3))(2)](ClO(4))(6)·(H(5)O(2))(3) reveals an octahedral co-ordination at the Ni centre, while the crystal structure of [Ni(III)(bis[9]aneNS(2)-C(2)H(4))](ClO(4))(6)·(H(3)O)(3)·3H(2)O exhibits a more distorted co-ordination. In the homoleptic analogue, [Ni(III)([9]aneS(3))(2)](ClO(4))(3), structurally characterized at 30 K, the Ni-S distances [2.249(6), 2.251(5) and 2.437(2) Å] are consistent with a Jahn-Teller distorted octahedral stereochemistry. [Ni([9]aneNS(2)-CH(3))(2)](PF(6))(2) shows a one-electron oxidation process in MeCN (0.2 M NBu(4)PF(6), 293 K) at E(½)=+1.10 V versus Fc(+)/Fc assigned to a formal Ni(III)/Ni(II) couple. [Ni(bis[9]aneNS(2)-C(2)H(4))](PF(6))(2) exhibits a one-electron oxidation process at E(½)=+0.98 V and a reduction process at E(½)=-1.25 V assigned to Ni(II)/Ni(III) and Ni(II)/Ni(I) couples, respectively. The multi-frequency X-, L-, S-, K-band EPR spectra of the 3+ cations and their 86.2% (61)Ni-enriched analogues were simulated. Treatment of the spin Hamiltonian parameters by perturbation theory reveals that the SOMO has 50.6%, 42.8% and 37.2% Ni character in [Ni([9]aneNS(2)-CH(3))(2)](3+), [Ni(bis[9]aneNS(2)-C(2)H(4))](3+) and [Ni([9]aneS(3))(2)](3+), respectively, consistent with DFT calculations, and reflecting delocalisation of charge onto the S-thioether centres. EPR spectra for [(61)Ni([9]aneS(3))(2)](3+) are consistent with a dynamic Jahn-Teller distortion in this compound.