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| Synthesis and Characterization. Reaction of [RuII(PPh3)3Cl2] with MeQH in the presence of Et3N in MeOH produces a neutral carbonyl hydrido complex [RuII(MeQ)(PPh3)2(CO)(H)] (1). Under similar reaction conditions using [RuII{P(C6H4Me)3}3Cl2] or [RuII{P(C6H4OMe)3}3Cl2] in place of [RuII(PPh3)3Cl2] also afforded the target carbonyl hydrido complexes with the corresponding phosphine ligands, [RuII(MeQ){P(C6H4Me)3}2(CO)(H)] (2) and [RuII(MeQ){P(C6H4OMe)3}2(CO)(H)] (3), respectively (Scheme 1a). The carbonyl and hydride ligands of these complexes are derived from the decarbonylation of primary alcohol (MeOH). Similar decarbonylation of methanol, such as the formation of carbonyl hydrido complex [RuII(PPh3)3(CO)(Cl)(H)] from the reaction between 16e– ruthenium complex [RuII(PPh3)3(Cl)2] and MeOH in the presence of base,11 are commonly reported in other transition metals complexes, in particular for those with 16e– Ru(II) metal center.[ (a) Bennet, M. A.; Bruce, M. I.; Matheson, T. W. In Comprehensive Organometallic Chemistry; Wilkinson, G.; Stone, F. G. A.; Abel, E. W.; Eds.; Pergamon Press: Oxford, U.K., 1982, Vol. 4, pp 721. (b) Chatt, J.; Shaw, B. L.; Field, A. E. J. Chem. Soc. 1964, 3466. (c) Benedetti, E.; Braca, G.; Sbrana, G.; Salvetti, F.; Grassi, B. J. Organomet. Chem. 1972, 37, 361. (d) Empsall, H. D.; Hyde, E. M.; Mentzer, E.; Shaw, B. L.; Uttley, M. F. J. Chem. Soc., Dalton Trans. 1976, 2069. (e) Chaudret, B. N.; Cole-Hamilton, D. J.; Nohr, R. S.; Wilkinson, G. J. Chem. Soc., Dalton Trans. 1977, 1546. (f) Cole- Hamilton, D. J.; Wilkinson, G. Nouv. J. Chim. 1977, 1, 142. (g) Gill, D. F.; Shaw, B. L. Inorg. Chim. Acta 1979, 33, 19. (h) Morton, D.; Cole-Hamilton, D. J.; Utuk, I. D.; Paneque-Sosa, M. J. Chem. Soc., Dalton Trans. 1989, 489. (i) Portnoy, M.; Frolow, F.; Milstein, D. Organometallics 1991, 10, 3960.] To elucidate the role of methanol in the formations of these carbonyl hydrido complexes, the reaction between the [RuII(PPh3)3Cl2] and MeQH was also carried out in ethanol. The major product was then characterized to be the carbonyl methyl complex [RuII(MeQ)(PPh3)2(CO)(CH3)] (4), which is an air-stable and diamagnetic. This reaction is similar to the formation of corresponding carbonyl methyl complex [TpRuII(CH3)(CO)(PPh3)] from the reaction of [(Tp)RuIICl(PPh3)(CH3CN)] (Tp = hydrotris(pyrazolyl)borate) with NaBH4 in EtOH.[ Chen, Y.-Z.; Chan, W. C.; Lau, C. P.; Chu, H. S.; Lee, H. L. Organometallics 1997, 16, 1241.] When the reaction of [RuII(PPh3)3Cl2] with MeQH was carried out in nPrOH, it also produces the ethyl carbonyl complex [RuII(MeQ)(PPh3)2(CO)(CH2CH3)]. However, the ethyl carbonyl complex is unstable in solution, presumably, due to spontaneous β-H elimination of Ru-CH2CH3 to form an alkene complex. On the other hand, when the reaction was carried out in PhCH2OH, it produced exclusively [RuII(MeQ)(PPh3)2(CO)(H)] (1) rather than [RuII(MeQ)(PPh3)2(CO)(Ph)]. |
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8814402
至尊木虫 (职业作家)
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756762952: 金币+30, 翻译EPI+1, ★★★★★最佳答案 2012-05-15 10:13:23
756762952: 金币+30, 翻译EPI+1, ★★★★★最佳答案 2012-05-15 10:13:23
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合成和表征 [RuII(PPh3)3Cl2] 和 MeQH 在含有三乙胺的甲醇中反应生成一种中性羰基氢化络合物[RuII(MeQ)(PPh3)2(CO)(H)](1)。在相似的反应条件下，用[RuII{P(C6H4Me)3}3Cl2] 或[RuII{P(C6H4OMe)3}3Cl2] 代替[RuII(PPh3)3Cl2] ，也分别得到具有相应膦配体的目标羰基氢化络合物RuII(MeQ){P(C6H4Me)3}2(CO)(H)] (2) 和 [RuII(MeQ){P(C6H4OMe)3}2(CO)(H)] (3)。 这些络合物的羰基和氢化物配体源自于伯醇（甲醇）的脱羧作用。 甲醇的相似的脱羧作用，诸如由16e–钌络合物 [RuII(PPh3)3(Cl)2]和甲醇在碱性条件下反应生成羰基氢化络合物[RuII(PPh3)3(CO)(Cl)(H)]，11在其它过渡金属络合物中经常有报道，尤其是那些具有16e– Ru(II) 金属中心者为了阐明甲醇在这些羰基氢化络合物的生成反应中的作用，[RuII(PPh3)3Cl2]和 MeQH 间的反应也在乙醇中进行了试验。主要的反应产物经表征为羰基甲基络合物[RuII(MeQ)(PPh3)2(CO)(CH3)] (4)，此络合物在空气中稳定，具有反磁性。 这一反应与通过[(Tp)RuIICl(PPh3)(CH3CN)] 和NaBH4 在乙醇中生成相应的羰基甲基络合物[TpRuII(CH3)(CO)(PPh3)] 的反应相似。当[RuII(PPh3)3Cl2] 和 MeQH 的反应在nPrOH （正丁醇）中进行时，也生成了乙基羰基络合物[RuII(MeQ)(PPh3)2(CO)(CH2CH3)]。然而，此乙基羰基络合物在溶液中不稳定，推测可能是由于Ru-CH2CH3的自发β-H 消除形成了烯烃络合物。反过来说，当反应在苯甲醇中进行时，专一性地生成[RuII(MeQ)(PPh3)2(CO)(H)] (1)，而非[RuII(MeQ)(PPh3)2(CO)(Ph)]. |
2楼2012-05-15 09:22:41
8814402
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3楼2012-05-15 09:24:21
