Oxazoles XXII.* The Cobalt(ii) Coordination Chemistry of 2-(ortho-Anilinyl)-4,4-dimethyl-2-oxazoline: Syntheses, Properties, and Solid-State Structural Characterization

Ethanol solutions of the cobalt(ii) halides react with an excess of 2-(ortho-anilinyl)-4,4-dimethyl-2-oxazoline (1: i.e. 2-(2′-anilinyl)-4,4-dimethyl-4,5-dihydro-1,3-oxazole) to give isolable κ2-N,N′-bonded species of 1 in good to excellent yields. The complexes CoX2(1-κ2-N,N′)·(H2O) n have been isolated for X = Cl (2: n = 1/2), X = Br and I (3 and 4, respectively; n = 0); the solid-state structures (X-ray) are in accordance with those suggested by UV-visible spectroscopy and conductivity measurements (i.e. non-ionic complexes with a pseudo-tetrahedral coordination motif around Co). In contrast, reaction of excess 1 with Co(NCS)2 forms the octahedral (UV-visible, X-ray) bis-isothiocyanato complex Co(NCS-κ1-N′)2(1-κ2-N,N′)2 (5) with cis-oriented NCS groups and trans-disposed oxazolines. Calculations at the PM3(tm) level of theory suggest that this isomer is close in energy to the four other possible (gas-phase) isomers. Treatment of ethanol solutions of hydrated cobaltous nitrate with excess 1 yields a material analyzed as [Co(NO3)(1)(H2O)2](NO3) (6a) and a small amount (less than 1%) of a second complex (6b); the latter has been characterized (X-ray) as the hydrated octahedral complex [Co(NO3-κ1-O)(1-κ2-N,N′)2(OH2)](NO3). In this case, the nitrato and aqua groupings are located cis to one another and trans to the coordinated –NH2 groups. Complex 6a is surmised to have a [Co(NO3-κ2-O,O′)2(1-κ2-N,N′)(OH2)2]NO3 structure. Cobalt compounds 2–5 and 1 have also been screened for their antifungal properties against Aspergillus niger, Aspergillus flavus, Candida albicans, and Saccharomyces cerevisiae but were found to be inactive in this regard.