The First Examples of Organometallic Crown Ethers Containing Redox-Active Tetrahedral Mo₂Fe(μ₃-S) Cluster Cores via a Novel Self-Assembly Cyclization Reaction

Three novel organometallic crown ethers with a general formula [Mo 2 Fe(μ 3 -S)(CO) 7 ] n [η 5 -C 5 H 4 CH 2 (CH 2 OCH 2 ) 3 CH 2 C 5 H 4 -η 5 ] n ( 3, n = 1; 4, n = 2; 5, n = 3) were synthesized through an unexpected cyclization reaction of [η 5 -C 5 H 4 CH 2 (CH 2 OCH 2 ) 3 CH 2 C 5 H 4 -η 5 ][(CO) 3 MoNa] 2 ( 1 ) with [MoCoFe(μ 3 -S)(CO) 8 ] 2 [η 5 -C 5 H 4 CH 2 (CH 2 OCH 2 ) 3 CH 2 C 5 H 4 -η 5 ] ( 2 ). The crystal structure of 3 and one of the possible pathways for formation of 3 − 5 are briefly discussed.