A revised synthesis of the hexadentate ligand 5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianon- ane-1,9-diamine (N3S3) is reported. Reaction between the sodium salt of 2-aminoethanethiol and 1,1,1-tris([( tolylsulfonyl )oxy]methyl)ethane in refluxing ethanol results in the formation of the hexadentate ligand N3S3. The preparation of the nickel(II) and cobalt(III) complexes is reported. The crystal structure of [Co(N3S3)](ClO4)3.H2O has been determined by X-ray diffraction methods and refined to a residual of 0.044 for 3696 independent observed reflections. The crystals are monoclinic, P21/n, a 9.314(4), b 15.581(6), c 17.026(3) Ǻ, β 90.30(4)°. Low temperature (c.10 K) absorption spectra are reported for [Co(N3S3)]3+ and the analogous encapsulated complex [Co(AMN3S3sarH)]4+ where both the spin-allowed 1A1g → 1T1g, 1T2g and spin-forbidden 1A1g → 3T1g, 3T2g were observed. Ligand -field calculations based on octahedral symmetry result in the ligand -field parameters B 461, C 3075, Dq 2303 cm-1, and B 462, C 3085, Dq 2266 cm-1 for the [Co(N3S3)]3+ and [Co(AMN3S3sarH)]4+ complexes, respectively. A systematic reduction occurs in the Racah B parameter of between 25 and 30 cm-1 for each additional thioether donor in the series of complexes N6-xSx (x = 0, 1, 2, 3). In addition, there is evidence for a progressive increase in the Racah C/B ratio with increasing number of thioether donors in this series.
Unusual Seven Coordination of Oxovanadium(V) Oximato Complex: Synthesis and X-Ray Crystal Structure