SYNTHESIS AND REACTIVITY OF CHIRAL METAL FLUORIDE AND WATER COMPLEXES DERIVED FROM THE RHENIUM FRAGMENT [(ETA-5-C5H5)RE(NO)(PPH3)]+
Academic Article
Overview
Identity
Additional Document Info
Other
View All
Overview
abstract
Reactions of triflate complex (5-C5H5)Re(NO)(PPh3)(OTf) (6), chlorobenzene complex [5-C5H5)Re(NO)(PPh3)-(C1C6H5)]+BF4-, and tetrahydrofuran complex [5-C5H5)Re(NO)(PPh3)(THF)]+BF4-with (Me2N)3S+[SiMe3F2]-give fluoride complex (5-C5H5)Re(NO)(PPh3)(F) (3) in 95% NMR yields. Analytically pure 3 can be isolated from the last reaction in 65-75% yields, but decomposes on the time scale of hours in solution. The reaction of 3 with BF3-OEt2(-95 to -40 C) gives the dichloromethane complex [(5-C5H5)Re(NO)(PPh3)(ClCH2Cl)]+BF4-(1), and that with MeOTf gives 6 and MeF. Reaction of 3 and P(p-tol)3gives mainly the fluoride ligand substitution product [()5-C5H5)Re(NO)(PPh3)(P(p-tol)3)]+X-. Reaction of 1 and H20 gives the water complex [(5-C5H5)Re(NO)(PPh3)(OH2)]+BF4-(4+BF4-, 87%), which in turn reacts with CH3CN (3 equiv) to give [(5-C5H5)Re(NO)(PPh3)(NCCH3)]+BF4-and H2O. Reaction of (5-C5H5)Re(NO)(PPh3)(H) with Ph3C+PF6-and then H2O gives 4+PF6-(91%). Reaction of (5-C5H5)Re(NO)(PPh3)(CH3) and aqueous HF appears to give water complex 4+X-(X-= F-or HF2-). Complex 3 is inert to water, but converts to 4+X-in the presence of HF or HBF4-OEt2. 1992, American Chemical Society. All rights reserved.
