| العنوان: |
Properties and crystal structure of square-planar R,S,R,S-(1,3,6,8,12,15-hexaazatricy clo[13.3.1.1 8,12]icosane)nickel(II) perchlorate and kinetics of its isomerization to the R,R,S,S configuration |
| مستخلص: |
The four-co-ordinate nickel(II) macrocyclic complex (R,S,R,S)-[NiL][ClO4] 2, where L is 1,3,6,8,12,15-hexaazatricyclo[13.3.1.1 8,12 ]icosane, has been isolated. It shows a significantly weaker ligand field with an increased absorption coefficient and more positive electrochemical oxidation and reduction potentials compared with those of the R,R,S,S isomer. Its crystal structure was determined by X-ray crystallography. It shows a square-planar geometry with a large tetrahedral distortion of the four nitrogen donors (maximum ± 0.135 Å). The average Ni–N bond distance is 1.938(3) Å for the secondary nitrogens and 1.969(3) Å for the tertiary. The complex isomerizes to the R,R,S,S complex at 50 °C in an aqueous solution containing 9.1% (v/v) MeCN. The first-order rate constant kobs is 4.16 × 10-5 s-1 at pH 7 and I = 1.0 mol dm-3 (LiClO4). The value of kobs is independent of pH and buffer concentration, but increases with increase in water content and decrease in ionic strength. The activation parameters are ΔH ‡ = 33 ± 1 kcal mol-1 and ΔS ‡ = 24 cal K-1 mol-1 at 25 °C. It is proposed that isomerization of the R,S,R,S to the R,R,S,S complex proceeds via axial co-ordination of water followed by a Ni–N(tertiary) bond dissociation assisted by a water molecule in the second co-ordination sphere acting as a general acid. |
