Activation of alkynols on transition metal carbonyl clusters. Reactions of1-ethynylcyclohexanol with Fe-3(CO)(12) and Co-2(CO)(8). Crystal structures of Co-3(CO)(9)[mu(3)-CCH2(C6H10OH)], Fe-3(CO)(9)(mu-CO)[mu(3)-eta(2)-C=C(C6H10)] and Co2Fe(CO)(6)(mu-CO)[mu(3)-eta(7)-(C6H9)CC(H)C(H)C(H)(C6H10)]

The reactions of Co-2(CO)(8) with 1-ethynylcyclohexanol (HC=CC6H10OH, ECY) in benzene led mainly to Co-2(CO)(6)(ECY) 1 and to smaller amounts of the m ethylidyne complex Co-3(CO)(9)[mu (3)-CCH2(C6H10OH)] 2. The reactions of Fe -3(CO)(12) with ECY in the same solvent led to binuclear metallacyclic deri vatives Fe-2(CO)(6)(ECY)(2) (isomers 3a, 3b) or Fe-2(CO)(6)[(ECY)(2)-H2O] 3 c as the main products; small yields of trinuclear complexes Fe-3(CO)(9)(mu -CO)[mu (3)-eta (2)-1,2-HC=C(C6H10OH)] 4 Fe-3(CO)(9)(mu -CO)[mu (3)-eta (2 )-1,2-C=C(C6H10)] 5 and Fe-3(CO)(7)[mu (3)-eta (7)-(C6H10OH)CCHCHC(C6H9)] 6 {containing respectively a parallel alkynol, an allenylidene and a dimeric metallacyclic ligand} were also obtained, together with 7, a thermal decom position product of 6. Finally, when Co-2(CO)(8) was treated with ECY in be nzene, and Fe-3(CO)(12) was added, the heterometallic complex Co2Fe(CO)(6)( mu -CO)[mu (3)-eta (7)-(C6H9)CC(H)C(H)C(H)(C6H10)] 8 was obtained in low yi elds. The complexes have been characterized by means of IR and H-1 NMR spec troscopies and by mass spectrometry. The structures of 2, 5, 8 have been de termined by X-ray diffraction. Complex 2 contains an "hydrogenated" ECY lig and, 5 an allenylidene ligand formed upon dehydration of ECY (loss of the O H and of the terminal hydrogen), whereas 8 contains a ligand formed by tail -to-tail coupling of two ECY molecules, with loss of water and oxygen and s hift of hydrogen. The elemental analysis of complex 8 gave a Co:Fe ratio of 2:1; on the basis of this analysis, the refinement of the diffraction data allowed a hypothesis on the distribution of the metal atoms in the cluster . Reaction pathways for the formation of these clusters are proposed and de hydration mechanisms for the ligand discussed.