Ralph J. Spohn

Co8(CO)24C6, a bis(tricobalt nonacarbonyl)/dicobalt hexacarbonyl derivative of 2,4-hexadiyne from the reaction of dicobalt octacarbonyl with hexachlorocyclopropane

Abstract The reaction of dicobalt octacarbonyl with hexachlorocyclopropane in THF produced Co 8 (CO) 24 C 6 whose structure (A) was determined by means of single crystal X-ray crystallography. The compound is obtained from hexane/benzene as black Co 8 (CO) 24 C 6 · 1 2 C 6 H 6 , crystallising in the triclinic space group P 1 with a = 15.57 ± 0.02 A, b = 16.32 ± 0.02 A, c = 9.77 ± 0.01 A, α = 99.78 ± 0.10°, β = 115.06 ± 0.10 °, γ = 74.39 ± 0.10 °. The final discrepancy index is R F = 10.25% for 2484 independent, nonzero reflections.

Organocobalt cluster complexes : XII. The arylation and alkylation of methylidynetricobalt nonacarbonyl with organomercury compounds☆

Abstract The reaction of diarylmercurials and arylmercuric halides with methylidynetricobalt nonacarbonyl in benzene or THF at reflux results in formation of benzylidynetricobalt nonacarbonyl complexes, ArCCo3(CO)9, in good yield, especially when the reactions are carried out under an atmosphere of carbon monoxide. The alkylation of HCCo3(CO)9 with dialkylmercurials or alkylmercuric halides proceeds much more slowly and in much lower yields. Similar reactions of (α-haloalkyl)mercurials, (RCHX)2Hg, with HCCo3(CO)9, gives reduced products, RCH2CCo3(CO)9, rather than the expected RCHXCCo3(CO)9. Similar arylation of the apical carbon atom of the CCo3 cluster occurred in the reactions of XCCo3(CO)9 (X = Cl, Br, I) with diphenylmercury, and in reactions of tetraphenyltin and tetraphenyllead with HCCo3(CO)9.