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From straight chain to macrocyclic complexes containing mixed sulfur/nitrogen donors and coordinated 1,3-diynes |
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| Authors: | Vladimir B Golovko Martin J Mays |
| Institution: | a Department of Chemistry, Lensfield Road, Cambridge CB2 1EW, UK b Department of Chemistry, Canterbury University, Private Bag 4800, Christchurch, New Zealand c Department of Chemistry, University of Leicester, University Road, Leicester LE1 7RH, UK |
| Abstract: | The acid-mediated reaction of {Co2(CO)6(μ-η2-HOCH2C C-)}2] (1) with the meta- and para-substituted aminothiophenols, 3-NH2-C6H4SH and 4-NH2-C6H4SH, affords the straight chain species, {Co2(CO)6(μ-η2-(3-NH2-C6H4S)CH2CC-)}2] (2) and {Co2(CO)6(μ-η2-(4-NH2-C6H4S)CH2CC-)}2] (3), respectively. The molecular structure of 3 reveals the presence of two isomeric forms differing in the relative disposition of the S-aryl groups. Conversely, reaction of 1 with the ortho-substituted aminothiophenol, 2-NH2-C6H4SH, furnishes the 10-membered macrocyclic species {Co2(CO)6}2{cyclo-μ-η2:μ-η2-CH2C2C2CH2SC6H3-NH-2}] (4) along with the linear chain complex {Co2(CO)6(μ-η2-(2-NH2-C6H4S)CH2CC-)}2] (5). On the other hand, treatment of 1 with the ortho-substituted mercaptopyridine, 2-SH-C5H4N, in the presence of HBF4 gives the salt {Co2(CO)6(μ-η2-(2-S-C5H4NH)CH2CC-)}2](BF4)2 (6a) in good yield; work-up in the presence of base affords the neutral complex {Co2(CO)6(μ-η2-(2-S-C5H4N)CH2CC-)}2] (6b). Single crystal X-ray diffraction studies have been reported on 3-5 and 6a. |
| Keywords: | Cobalt Coordinated 1 3-diyne Macrocycle Straight chain N-C bond formation Nicholas reaction |
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