名称:
Syntheses, spectroscopic characterization and electrochemical properties of organometallic crown ethers containing tetrahedral W2Fe(μ3-S) cluster cores [W2Fe(μ3-S)(CO)7][η5-C5H4CH2(CH2OCH2)nCH2C5H4-η5] (n=1–3). Crystal structures of [W2Fe(μ3-S)(CO)7][η5-C5H4CH2(CH2OCH2)nCH2C5H4-η5] (n=2,3)
摘要:
The self-assembly cyclization reactions of the ether chain-bridged dicyclopentadienyl W/Na salts Na-2[{W(CO)(3)}(2){eta (5)-C5H4CH2(CH2OCH2)(n)CH2C5H4-eta (5)}] (Ia-c, n = 1-3) with the same chain-bridged dicyclopentadienyl double clusters [WCoFe(mu (3)-S)(CO)(8)](2)[eta (5)-C5H4CH2(CH2OCH2)(n)CH2C5H4-eta (5)] (IIa-c, n=1-3) have been shown to give organometallic crown ethers [W2Fe(mu (3)-S)(CO)(7)][eta (5)-C5H4CH2 (CH2OCH2)(n)CH2C5H4-eta (5)] (IIIa-c, n =1-3). While structures of these new W2Fe(mu (3)-S) cluster crown ethers were fully characterized by elemental analyses, IR, H-1-NMR and FAB-MS spectroscopies, those of IIIb,c were unambiguously confirmed by X-ray diffraction techniques. In the study of possible pathway for the formation of ma-c, the new cluster crown ether me and its known Mo analog [Mo2Fe(mu (3)-S)(CO)(7)][eta (5)-C5H4CH2(CH2OCH2)(3)CH2C5H4-eta (5)] (IV) were also found to be formed through self-assembly cyclization reaction of the W/Na salt Na-2[{W(CO)(3)}(2){eta5-C5H4CH2(CH2OCH2)(3)CH2C5H4-eta (5)}] and the corresponding Mo-containing double cluster [MoCoFe(mu (3)-S)(CO)(8)](2)[eta (5)-C5H4CH2(CH2OCH2)(3)CH2C5H4-eta (5)]. In addition, the electrochemical properties of IIIa-c have been studied by cyclic voltammetric techniques. (C) 2000 Elsevier Science B.V. All rights reserved.