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ABSTRACT: The action of alkanethiols on bromomethylidynetricobalt nonacarbonyl in the presence of Et3N gives thioesters, RSC(O)CCo3(CO)9, as principal products, but arenethiols react to give tars. A more useful reaction is that between arenethiols and ClCCo3(CO)9, which gives ArSCCo3(CO)9 complexes as the principle products. The action of lithium alkane- and arenethiolates on BrCCo3(CO)9 in hydrocarbon medium gave thioesters, but in the presence of Et3N or Et2O, complexes Co3(CO)4(SR)5 are formed instead. Possible mechanisms of these reactions are discussed. [on SciFinder(R)]
J. Organomet. Chem. 01/1980; 187(1):91-102.
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ABSTRACT: The thermolysis of methylidynetricobalt nonacarbonyl, HCCo3(CO)9, in refluxing xylene soln. gives a mixt. of MeCCo3(CO)9 and EtCCo3(CO)9. A reaction course involving the generation of a carbyne and its addn. to the CCo3 core of the HCCo3(CO)9 mol., followed by extrusion of Co(CO)3 to give acetylenehexacarbonyldicobalt and finally decompn. of the latter to form MeCCo3(CO)9, is suggested. A sep. expt. confirmed that the last step can occur. [on SciFinder(R)]
J. Organomet. Chem. 01/1978; 162(1):89-98.
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ABSTRACT: Treating alkanethiols (e.g. Me3CSH) or Li alkanethiolates with bromomethylidynetricobalt nonacarbonyl gave (RSC(O)CCo3(CO)9 (I; R = e.g. Me3C). I (R = Ph) also was obtained by treating LiSPh with the cobalt complex; however, treating arenethiols with the cobalt complex or the analogous chloro compd. in the presence of Et3N gave ArSCCo3(CO)9 (Ar = aryl) and partial cluster degrdn. to give Co3(CO)4(SAr)5. Refluxing RSC(O)CCo3(CO)9 in benzene under N, gave decarbonylation products, RSCCo3(CO)9, in low yield. [on SciFinder(R)]
J. Organomet. Chem. 01/1978; 144(2):C26-C30.
