119480-28-3Relevant academic research and scientific papers
Preparation and characterization of W(OR)4Cl2 complexes (R = pentafluorophenyl, 2,6-dichlorophenyl) and some of their reduction products, including an X-ray study of W(O-2,6-C6H3Cl2)4Cl(Et2O)
Kolodziej, Richard M.,Schrock, Richard R.,Dewan, John C.
, p. 1243 - 1248 (2008/10/08)
WCl6 reacts with 4 equiv of pentafluorophenol in carbon tetrachloride to give W(OC6F5)4Cl2 in ～90% yield. W(OC6F5)4Cl2 can be reduced with 2 equiv of sodium amalgam in ether to give paramagnetic [Na(ether)x]2[W(OC6F5) 4Cl2] in ～65% yield. Cation exchange with either tetraphenylarsonium chloride or tetra-n-butylammonium bromide yields [AsPh4]2[W(OC6F5)4Cl 2] or [(n-Bu)4N]2[W(OC6F5) 4Cl2], respectively. WCl6 reacts with an excess of melted 2,6-dichlorophenol (HDCP) to give W(DCP)4Cl2 in ～65% yield. W(DCP)4Cl2 can be reduced with 1 equiv of sodium amalgam in ether to give paramagnetic W(DCP)4Cl(ether) in ～75% yield. W(DCP)4Cl(ether) belongs to the space group P2/n with a = 12.241 (9) ?, b = 8.643 (2) ?, c = 17.408 (8) ?, β = 102.25 (5)°, V = 1799.8 ?3, and Z = 2. Final R1 = 0.082 and R2 = 0.090. The complex is octahedral with the ether molecule trans to the chloride ligand. W(DCP)4Cl(pyridine), which is prepared from W(DCP)4Cl(ether) and 1 equiv of pyridine, and W(DCP)4Cl(ether) do not react further with 0.5% sodium amalgam. W(DCP)4Cl(PMe3), which is prepared from W-(DCP)4Cl(ether) and 1 equiv of PMe3, reacts with 1 equiv of sodium amalgam to yield paramagnetic W(DCP)4(PMe3) in ～65% yield. Cyclic voltammograms of W(OC6F5)4Cl2 and W(DCP)4Cl2 in dichloromethane consist of two reduction waves, the first of which is at best only quasi-reversible. The cyclic voltammogram of W(DCP)4Cl(pyridine) in dichloromethane consists of one oxidation and one reduction wave, which appear to be reversible at scan speeds of 10-200 mV s-1.
