In this project the synthesis and characterization of the complexes with possible bio- and electro- or photochemical applications have been discussed. ( 1 ) [Co(Me-Saldien)(4-MePy)]B(Ph) 4 ; ( 2 ) [Co(Me-Saldien)(4-MePy)]B(Ph) 4 ; ( 3 ) [Co(Me-Saldien)( Py)]B(Ph) 4 ( 4 ) [Co(Me-Saldien)(1-MeIm)]B(Ph) 4 ; ( 5 ) [Co(Me-Salbn)(py)]BPh 4 ( 6 ) [Co(Me-Salbn)(4-MePy)]BPh 4 ; The complexes, ( 1 ) to ( 6 ) are synthesized in good yield and are characterized by FT-IR, UV-Vis and 1 H-NMR spectroscopy and elemental analyses. The structure of complex ( 6 ) have been determined by X-ray crystallography, and the correlation between structural and spectroscopic properties are discussed. In conclusion, the steric effects on the structural properties of these complexes are discussed and compared with those of similar complexes synthesized.