Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H2)(PPh3) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction
Synthesis of Alkyl- and Aryl[hydrotris(pyrazolyl)borato]carbonylruthenium Complexes by Decarbonylation of Alcohols. Synthesis of TpRuH(H2)(PPh3) [Tp = Hydrotris(pyrazolyl)borate], an Observable Intermediate in the Decarbonylation Reaction
复制标题
通过醇脱羰合成烷基和芳基[氢三(吡唑基)硼]羰基钌配合物。
DOI：
10.1021/om960817u
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发表时间：
1997
期刊：
影响因子：
2.8
通讯作者：
G. Jia
中科院分区：
文献类型：
--
作者：
Yuzhong Chen;WaiChung Chan;C. Lau;H. Chu;Hin Ling Lee;G. Jia
在乙醇中，TpRuCl(PPh_3)(CH_3CN)(Tp=氢化(吡唑基)硼酸盐)与NaBH_4反应没有得到预期的氢化物络合物TpRuH(PPh_3)(CH_3CN)(2)，而是甲基羰基络合物TpRu(CH_3)(CO)(PPh_3)(1b)。1b的形成是由于TpRuCl(PPh3)(CH3CN)在NaBH4还原过程中原位生成的2与乙醇的脱羰反应所致。在其他伯醇RCH2OH(R=H、C2H5、n-C3H7、C6H5、C6H4CH3-4和C6H4Cl4)的存在下，类似的反应生成了相应的σ-有机络合物TpRuR(CO)(PPh3)。反应的一个共同特征是醇的RCH2OH的R基团成为最终金属络合物中的σ-有机基团。提出了金属−η-2-醛和−η-2-二氢中间体参与的脱羰反应机理。观察到η-2-二氢络合物TpRuH(H2)(PPh_3)(3)在脱羰反应中的存在，证实了这一点。...=‘class1’>40大气压下加热2的四氢呋喃溶液，在60°C的氢气中加热48h，或在
Treatment of TpRuCl(PPh3)(CH3CN) (Tp = hydrotris(pyrazolyl)borate) with NaBH4 in ethanol did not yield the expected hydride complex TpRuH(PPh3)(CH3CN) (2) but rather the methyl carbonyl complex TpRu(CH3)(CO)(PPh3) (1b). Formation of 1b was due to decarbonylation of ethanol by 2 generated in situ by NaBH4 reduction of TpRuCl(PPh3)(CH3CN). Analogous reactions in the presence of other primary alcohols RCH2OH (R = H, C2H5, n-C3H7, C6H5, C6H4CH3-4, and C6H4Cl-4) led to the corresponding σ-organyl complexes TpRuR(CO)(PPh3). A common feature of the reactions is that the R groups of alcohols RCH2OH become the σ-organyl groups in the final metal complexes. A mechanism involving metal−η2-aldehyde and −η2-dihydrogen intermediates is proposed for the decarbonylation reaction. This is supported by the observation of the η2-dihydrogen complex TpRuH(H2)(PPh3) (3) during the decarbonylation reaction. 3 was synthesized independently by heating a THF solution of 2 under 40 atm of H2 at 60 °C for 48 h or by heating 2 in CH3...