C-F Bond Activation of P(C6F5)3 by Ruthenium Dihydride Complexes: Isolation and Reactivity of the "Missing" Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF.
C-F Bond Activation of P(C6F5)3 by Ruthenium Dihydride Complexes: Isolation and Reactivity of the "Missing" Ru(PPh3)3H(halide) Complex, Ru(PPh3)3HF.
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DOI：
10.1021/acs.inorgchem.8b02286
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发表时间：
2018-10
影响因子：
4.6
通讯作者：
Mateusz K. Cybulski;Caroline J. E. Davies;J. Lowe;M. Mahon;M. Whittlesey
中科院分区：
文献类型：
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作者：
Mateusz K. Cybulski;Caroline J. E. Davies;J. Lowe;M. Mahon;M. Whittlesey
Ru（IMe 4）2（PPh 3）2 H2（1; IMe 4 = 1，3，4，5-四甲基咪唑-2-亚基）与P（C6 F5）3（PCF）反应的主要产物是五配位配合物Ru（IMe 4）2（PF 2 {C6 F5}）（C6 F5）H（2），它是通过一系列复杂的C-F/P-C键断裂和P-F键形成步骤形成的。相比之下，PCF中所有六个邻位C-F键的加氢脱附与Ru（PPh 3）4 H2一起发生，得到Ru（PPh 3）3 HF（3）。NaBArF 4夺取3中的氟化物配体，得到[Ru（{η6-C6 H5} PPh 2）（PPh 3）2 H][BArF 4]，而B2 pin 2与C6 D 6中的3反应，得到[Ru（{η6-C6 D 6）（PPh 3）2 H]+和Ru（PPh 3）4 H2的混合物。用HBpin（5当量）和HSiR 3（R = Et，Ph; 2当量）处理3分别得到Ru（PPh 3）3（σ-HBpin）H2和Ru（PPh 3）3（SiR 3）3 H3。当3与Me 3SiX（X = CF 3，C6 F5）反应时，没有产生稳定的取代产物。
The major product of the reaction between Ru(IMe4)2(PPh3)2H2 (1; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) and P(C6F5)3 (PCF) is the five-coordinate complex Ru(IMe4)2(PF2{C6F5})(C6F5)H (2), which is formed via a complex series of C-F/P-C bond cleavage and P-F bond formation steps. In contrast, hydrodefluorination of all six ortho C-F bonds in PCF occurs with Ru(PPh3)4H2 to afford Ru(PPh3)3HF (3). NaBArF4 abstracted the fluoride ligand in 3 to give [Ru({η6-C6H5}PPh2)(PPh3)2H][BArF4], while B2pin2 reacted with 3 in C6D6 to yield a mixture of [Ru({η6-C6D6)(PPh3)2H]+ and Ru(PPh3)4H2. The treatment of 3 with HBpin (5 equiv) and HSiR3 (R = Et, Ph; 2 equiv) afforded Ru(PPh3)3(σ-HBpin)H2 and Ru(PPh3)3(SiR3)3H3, respectively. No stable substitution products were generated when 3 was reacted with Me3SiX (X = CF3, C6F5).