Complexes of High-Valent Rhenium Supported by the PCP Pincer

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• 作者：Alex J. Kosanovich ; Joseph H. Reibenspies ; Oleg V. Ozerov
• 刊名：Organometallics
• 出版年：2016
• 出版时间：February 22, 2016
• 年：2016
• 卷：35
• 期：4
• 页码：513-519
• 全文大小：348K
• ISSN：1520-6041

文摘

The PCP ligand can be introduced into the coordination sphere of Re by metalation in a reaction with L₂Re(O)Cl₃ precursors, leading to an octahedral (PCP)Re(O)Cl₂ (2), in which the aryl donor of PCP is cis to the oxo ligand. Halide exchange with Me₃SiBr or Me₃SiI furnished analogous (PCP)Re(O)Br₂ (3) and (PCP)Re(O)I₂ (4). Treatment of 2 with LiAlH₄ resulted in the isolation of (PCP)ReH₆ (5) upon workup. NMR data suggest a classical hexahydride nature for 5. 5 reacted with PMe₃ and 4-dimethylaminopyridine (DMAP) by losing H₂ and forming adducts (PCP^iPr)ReH₄(PMe₃) (6) and (PCP)ReH₄(DMAP) (7). On the other hand, reaction of 5 with CO resulted in loss of all the hydrides and formation of the Re(I) compound (PCP^iPr)Re(CO)₃ (8). Finally, thermolysis of the hexahydride 5 led to loss of half the hydrides as H₂ and formation of the dimeric species formulated as (PCP^iPr)₂Re₂H₆ (9).