Synthesis, structure and reactivity of [ReH2(NR) (Cyttp)]+ (Cyttp = PhP(CH2CH2CH2PCy2)2) complexes. Organoimido analogues of the oxo complex that transfers the elements of water to substrates
摘要:
The cationic organoimido-hydrido complexes [ReH2(NR)(Cyttp)](+) where R=NC6H4Me-p (2), Ph (3), Cy (4) and Cyttp=PhP(CH2CH2CH2PCy2)(2) were synthesized by reaction of [ReH2(O)(Cyttp)]O3SCF3 (1(Tf)) with the appropriate primary amine. Use of molecular sieves promotes the formation of these rhenium products. 2-4 were shown by H-1 NMR spectroscopy to contain two inequivalent, cis hydride ligands. An X-ray diffraction study of 2(PF6) revealed the presence of distorted mer-Cyttp and the organoimido ligand cis to all three phosphorus atoms. The hydride ligands were not located. Unlike its oxo-hydrido analogue, 1(SbF6),2(Tf) failed to react with CO or SO2 under comparable, or even more forcing, conditions. However, with anhydrous HCl it afforded ReCl3(Cyttp), and with NaBH4, ReH5(Cyttp).