Cobalt compounds sulfide derivatives

Solid-state sulfide compounds MMo2S4 (M = V, Cr, Fe, Co) contain infinite chains of Mo4S6 clusters with intracluster Mo-Mo distances (2.756-2.989 A) and intercluster distance (2.960 A) for the cobalt derivative (112). As the valence of M is +2, judging from magnetic measurements, and the average oxidation state of molybdenum +3, the CVE for M2Mo4S8 is 12. This agrees with five intracluster and one intercluster... 

Both of the above approaches employed a metal ion as a template about which the corrin cyclization was performed, but the nickel or cobalt ions could not subsequently be removed. In order to obtain metal-free corrins, a new route was therefore devised (67AG865) which employed the novel principle of sulfide contraction (Scheme 22). Thus the sodium salt of the precorrin (284) (Scheme 23) was transformed into the thiolactam (285), and loose complexation with zinc(II) ions caused cyclization to give (286), which was treated with benzoyl peroxide and acid to give the ring-expanded compound (287). Contraction with TFA/DMF gave the corrins (288) and (289), and the major of these (289) was desulfurized with triphenylphosphine and acid to give (288). Finally, demetallation with TFA gave the required metal-free corrin (290), a source for a whole variety of metal derivatives. 

Bromobis[2,3-butanedione dioximato( 1 -)] (4-terf-butylpyridine)cobalt(lIl) is a tan, microcrystalline solid with greatly enhanced solubility in organic solvents compared to the chloro(pyridine) analogue. It is also the compound of choice in preparing alkylcobaloximes by the subsequent procedure because of the ease of isolation of the resultant products. In addition, the bromo(4-ferf-bupy) species react directly with electron-rich olefins, such as ethyl vinyl ether, in the presence of ethanol to yield, in this case, bis[2,3-butanedione dioximato(l-)]-(2,2-diethoxyethyl)(pyridine)cobalt(III).1J Conversion of the dimethyl sulfide compound to the pyridine derivatives is readily detected by a characteristic infrared absorption at 1600 cm 1 (pyridine stretch). The H nmr spectrum of bromobis[2,3-butanedione dioximato(1 -)] (4-ferf-butylpyridine)cobalt (III) has absorptions in the alkane region in the ratio of 3 4 at 6 1.25 ppm [Py—C (CH3)3 ] and 6 2.43 ppm (dh—CH3) from tetramethylsilane. 

Within this field, many basic investigations and proposals for practical application have been made by Shirai et al. l They have investigated tetra- and octa-carboxylic acid derivatives of iron phthalocyanine and cobalt phthalocyanine, and found that catalytic activity is affected by the states of electron spins of metal ions and inactivated by formation of the mu-oxo dimer. Iron and cobalt ion in high spin states are more reactive than that in low spin states. High spin states of metal ions are achieved by modification of ligands. Shirai et al. have applied these materials as fiber deodorizers for such odors as ammonia, trimethylamine, hydrogen sulfide, and methanethiol, in which the phthalocyanine compounds are supported on fibers of cotton, wool, rayon, and artificial fibers. 

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