The self-assembly cyclization reactions of the ether chain-bridged dicyclopentadienyl Mo/Na salts [NaMo(CO) 3] 2[η 5-C 5H 4CH 2(CH 2OCH 2) n CH 2C 5H 4-η 5] ( Ia-d, n=1–4) with the same chain-bridged dicyclopentadienyl double clusters [MoCoFe(μ 3-S)(CO) 8] 2[η 5-C 5H 4CH 2(CH 2OCH 2) n CH 2C 5H 4-η 5] ( Iia– d, n=1–4) have been found, depending on the lengths of the bridged ether chains in starting materials I and II, to give several different types of novel organometallic macrocyclic crown ethers. While reaction of the Mo/Na salts ( I, n=1, 4) with double clusters ( II, n=1, 4) produced single Mo 2Fe(μ 3-S) cluster crown ethers [Mo 2Fe(μ 3-S)(CO) 7][η 5-C 5H 4CH 2(CH 2OCH 2) n CH 2C 5H 4-η 5] ( IIIa, n=1; IIId, n=4), the Mo/Na salts ( I, n=2, 3) reacted with double clusters ( II, n=2, 3) to afford single, double and triple Mo 2Fe(μ 3-S) cluster crown ethers [Mo 2Fe(μ 3-S)(CO) 7] m [η 5-C 5H 4CH 2(CH 2OCH 2) n CH 2 C 5H 4-η 5] m ( IIIb, n=2, m=1; IIIc, n=3, m=1; IVb, n=2, m=2; IVc, n=3, m=2; Vb, n=2, m=3; Vc, n=3, m=3), respectively. While structures of IIIa– d, IVb, c and Vb, c were characterized fully by elemental analyses, IR, 1H-NMR and FAB-MS spectrocopies, those of IIIa– c were further confirmed by X-ray diffraction techniques. In addition, the electrochemical properties of IIIa– d, IVb, c and Vb, c have been studied using cyclic voltammetry.
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