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34948874496
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34948837021
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12) The related η5-C5R5-type Rh complex 26 was also prepared following the procedures reported for the η5-C5Me5 derivative (Kang, J. W, Moseley, K, Maitlis, P. M. J. Am. Chem. Soc. 1969, 91, 5970, Successive treatment of 20 with RhCl3·3H2O (in refluxing methanol) and PPh3 (in diethyl ether at r.t, gave 26 as red powder, which was characterized spectroscopically. In a manner similar to 12 and 13, UV light irradiation of 26 caused appearance of a weak UV-vis shoulder band around 600 nm, which disappeared upon subsequent visible light irradiation (Figure S8, while no apparent change was detected by 1H NMR. 26: δH(CDCl3) 7.60 (14H, br, Ph, 7.35 (8H, br, Ph, 7.23 (8H, br, Ph, 7.11 (2H, s, Th, 2.08 (6H, s, Me-Th, 1.54 (12H, d, J, 4.6, C5Me4, 1.37 12H, d, J, 2.7, C
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-1): 419, 280 nm.
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62
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34948818931
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Preparation of a less sterically hindered indenyl derivative was attempted as shown below but unsuccessful. Via route 1, the desired product was formed but could not be separated from a mixture containing the monoindenyl compound and the starting compound. For route 2, although the intermediate corresponding to 17 could be obtained, subsequent lithiation with n-BuLi was followed by proton-transfer to give the debrominated product, as confirmed by D2O quenching. The less acidic C5Me4-H proton in 17 was resistant to the proton transfer, and therefore, 20 was obtained successfully. Image presented
-
4-H proton in 17 was resistant to the proton transfer, and therefore, 20 was obtained successfully. Image presented.
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63
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0001033532
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34948855024
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Because the thiophene part may participate in the reaction with Ru 3(CO)12, a preliminary experiment using a simpler thiophene-containing substrate was carried out and the expected product was obtained successfully and characterized spectroscopically (δH (CDCl3) 6.99, 6.72 (2H × 2, m × 2, Th, 2.49 (6H, s, Me-Th, 1.95, 1.77 (12H × 2, s × 2, C5Me4, IR (CH2Cl2) 1932, 1763 cm-1, But attempted preparation of the Cp*RuCl-(PPh3)2-type complex by successive treatment of the simpler thiophene with RuCl3· nH2O (in refluxing EtOH) and PPh3 resulted in the formation of a small amount of unidentified products. Image presented
-
3 resulted in the formation of a small amount of unidentified products. Image presented
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