Abstract
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 (PCPiPr)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 (PCPiPr)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 (PCPiPr)2Re2H6 (9).
Published Version
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