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

Abstract

Thermal reactions of Cp 2Mo 2(CO) 4(μ-η 2-C 14H 20) ( 1) with Fe 3(CO) 12 and Ru 3(CO) 12 produce [Cp 2Mo 2(CO) 4](μ,μ 3-η 2,η 2-C 14H 20)[Fe 3(CO) 9] ( 2) and [Cp 2Mo 2(CO) 4](μ,μ 3-η 2,η 3-C 14H 19)[(μ-H)Ru 3(CO) 9] ( 3-allyl), respectively, while treatments of 1 with Ru 3(CO) 10(NCMe) 2 and Os 3(CO) 10(NCMe) 2 afford [Cp 2Mo 2(CO) 4](μ,μ 3-η 2,η 3-C 14H 19)[(μ-H)Ru 3(CO) 9] ( 3-allenyl) and [Cp 2Mo 2(CO) 4](μ,μ 3-η 2,η 2-C 14H 20)[Os 3(CO) 10] ( 4), respectively. The allene moiety of 3-allenyl rearranges upon heating to give the allyl complex 3-allyl. Compound 1 reacts with Co 2(CO) 8 to produce [Cp 2Mo 2(CO) 4](μ,μ-η 2,η 2-C 14H 20)[Co 2(CO) 6] ( 5) and the reaction of Os 3(CO) 10(μ 3-η 2-C 14H 20) with Co 2(CO) 8 affords [Os 3(CO) 10](μ 3,μ-η 2,η 2-C 14H 20)[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 semibridging carbonyl connected to the Os 3 cluster.