Preparation of Mo, Co and iron group heterometallic clusters linked by cyclotetradeca-1,8-diyne ligand

Thermal reactions of Cp2Mo2(CO)(4)(mu-eta(2)-C14H20) (1) with Fe-3(CO)(12) and Ru-3(CO)(12) produce [Cp2Mo2(CO)(4)](mu,mu(3)-eta(2),eta(2)-C14H20)[Fe- 3(CO)(9)] (2) and [Cp2Mo2(CO)(4)](mu,mu(3)-eta(2),eta(3)-C14H19)[(mu-H)Ru-3 (CO)(9)] (3-allyl), respectively, while treatments of 1 with Ru-3(CO)(10)(N CMe)(2) and Os-3(CO)(10)(NCMe)(2) afford [Cp2Mo2(CO)(4)](mu,mu(3)-eta(2),et a(3)-C14H19)[(mu-H)Ru-3(CO)(9)] (3-allenyl) and [Cp2Mo2(CO)(4)](mu,mu(3)-et a(2),eta(2)-C14H20)[Os-3(CO)(10)], respectively. The allene moiety of 3-all enyl rearranges upon heating to give the allyl complex 3-allyl. Compound 1 reacts with Co-2(CO)(8) to produce [Cp2Mo2(CO)(4)](mu,mu-eta(2),eta(2)-C14H 20)[Co-2(CO)(6)] (5) and the reaction of Os-3(CO)(10)(mu(3)-eta(2)-C14H20) with Co-2(CO)(8) affords [Os-3(CO)(10)](mu(3),mu-eta(2),eta(2)-C14H20)[Co-2 (CO)(6)] (6). The new compounds 2-6 have been characterized by mass, IR and NMR spectroscopy. The crystal structure of 4 reveals a bridging and a semi bridging carbonyl connected to the Os-3 cluster. (C) 1999 Elsevier Science S.A. All rights reserved.