M. Kita, K. Yamanari, Y. Shimura
1989
Citations
0
Influential Citations
13
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
A series of mixed complexes [Co(pyt)3−n (diamine)n]n+ (n=0, 1, and 2; pyt=2-pyridinethiolate(1—) and diamine=ethylenediamine, (R)-propylenediamine, or 2,2′-bipyridine) have been prepared and characterized by means of their visible and ultraviolet absorption, circular dichroism, and magnetic circular dichroism spectra. In the [Co(pyt)3] or [Co(pyt)2(diamine)]+ complex, only one geometrical isomer, mer(S) or trans(S) respectively, has been obtained. The [Co(pyt)(en)2](ClO4)2 complex, which was spontaneously resolved, had an orthorhombic space group of P212121, with a=12.406(1), b=12.754(1), c=11.621(4) A, V=1838.7(6) A3, and Z=4. The refinement of 2276 reflections (Mo Kα radiation) led to R=0.049. The Co–N bond trans to the pyt sulfur atom was longer by 0.023(11) A than the cis one. The novel oxidation product [Co(2-pyridinesulfenato-N,S)(en)2]2+ was photochemically converted into the N,O-chelated linkage-isomer [Co(2-pyridinesulfenato-N,O)(en)2]2+ in the solid state, accompanied by ring-expansion from a fo...