Structures of bis(N-n-butylsalicylideneiminato)cobalt(II) and bis(N-tert-butylsalicylideneiminato)cobalt(II) complexes and reactivity towards oxygen and nitric oxide
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The cobalt(II)-Schiff base complexes [Co(nbsal)2] and [Co(tbsal)2] [nbsal=N-n-butylsalicylideneiminate and tbsal=N-tert-butysalicylideneiminate,o-OC6H4CH=NR,R+Bun and But, respectively] both have distorted tetrahedral structures, but the presence of thetert-butyl groups in [Co(tbsal)2] causes much greater angular distortion, of the coordination tetrahedron. Although [Co(nbsal)2] will react with nitric oxide and oxygen, [Co(tbsal)2] reacts with neither and this appears to be due to the shielding of the cobalt by thetert-vutyl groups. The reactive complex [Co(nbsal)2] crystallizes in the tetragonal system,a+14.244,c+5.395, Å,Z+2 and space group\(P\bar 4\). The structure was determined by the heavy-atom method, using MoKα diffractometer data, and refined by full matrix least-squares toR+0.035 for 777 reflections. The unreactive complex [Co(tbsal)2] crystallizes in the orthorhombic systemPbc21,a+10.977,b+20.037,c+9.866 Å,Z+4. The structure was determined as above toR+0.051 for 1458 reflections.
KeywordsOxygen Reflection Nitric Oxide Cobalt Inorganic Chemistry
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