Preparation and stereochemistry of bis(ethylenediamine)cobalt(III) complexes with selenium donor atom.

Five optically active cobalt(III) complexes of [Co(bidentate-N,Se)(en)2] type were prepared; here bidentate-N,Se denotes 2-aminoethaneselenolato (aes), 2-aminoethaneselenenato (aesee), 2-(methylseleno)ethylamine (mseea), 2-(ethylseleno)ethylamine (eseea), and 2-(benzylseleno)ethylamine (bseea). These complexes were characterized from their absorption, CD and 1H NMR spectra. Of these complexes, the crystal structure of (+)500CD-[Co(mseea)(en)2](ClO4)3 was determined by the X-ray diffraction method. The red plate crystal was orthorhombic, space group P212121, a=12.220(15), b=19.224(7), c=8.977(11) A, Z=4, and the final R value was 0.087. The coordinated selenium atom takes the (R) configuration for the Λ isomer. The absorption and CD spectra of the five complexes are discussed in comparison with those of the corresponding cobalt(III) complexes containing a coordinated sulfur atom.

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