1. The First Examples of Organometallic Crown Ethers Containing Redox-Active Tetrahedral Mo2Fe(μ3-S) Cluster Cores via a Novel Self-Assembly Cyclization Reaction
2. Supramolecular Chemistry
3. Metal Encapsulating Carbon Nanostructures from Oligoalkyne Metal Complexes
4. Synthesis of1aand1bwas performed in Schlenk flasks under dry nitrogen. A mixture of Fe3(CO)12(1.00 g, 2.0 mmol), THF (30 mL), HSCH2(CH2OCH2)2CH2SH (0.18 g, 1.0 mmol) or HSCH2(CH2OCH2)3CH2SH (0.23 g, 1.0 mmol), and Et3N (0.28 mL, 2.0 mmol) was stirred at room temperature for ca. 0.5 h to give a brown-red solution containing the [Et3NH]+salt of the dianion [(μ-CO)Fe2(CO)6]2[(μ-SCH2(CH2OCH2)nCH2S-μ)] (m1,n= 2 or 3). To the solution was added CS2(0.24 mL, 4.0 mmol) and the mixture was stirred at room temperature for 0.5 h. Then, 1,4-(BrCH2)2C6H4(0.26 g, 1.0 mmol) for preparation of1aor I(CH2)4I (0.13 mL, 1.0 mmol) for preparation of1bwas added and the mixture was stirred at room temperature for 12 h. Solvent was removed under reduced pressure. The residue was subjected to TLC separation using CH2Cl2/petroleum ether (v/v = 3:2 or 2:1) as eluent. From the main red band1aor1bwas obtained as a red solid.1a: yield 0.144 g (15%); mp 104−106 °C. IR (KBr disk): νC⋮O2074 (s), 2018 (vs), 1981 (vs); νC-O1105 (m); νCS1014 (m) cm-1.1H NMR (CDCl3): 2.81 (br s, 4H, 2SCH2), 3.72−3.85 (m, 8H, 4CH2O), 4.20−4.45 (m, 4H, 2SCH2Ar), 7.15 (s, 4H, C6H4) ppm.1b: yield 0.110 g (11%); mp 107−108 °C. IR (KBr disk): νC⋮O2066 (vs), 2024 (vs), 1993 (vs); νC-O1107 (m); νCS1017 (m) cm-1.1H NMR (CDCl3): 1.68 (br s, 4H, SCH2CH2CH2CH2S), 2.80 (br s, 8H, 4SCH2), 3.65−4.05 (m, 12H, 6CH2O) ppm.