Multiple Bonds between Main-Group Elements and Transition Metals. 138. Polymeric Methyltrioxorhenium: Some Models for Its Electronic Structure

Methyltrioxorhenium and its applications in olefin oxidation, metathesis and aldehyde olefination

“…At higher concentrations a second reaction, a faster reversible polymerization-precipitation, takes place to yield a golden colored solid of the empirical composition {H 0.5 [(CH 3 ) 0.92 ReO 3 ]} (poly-MTO) in about 70% yield (Eq. (1)) [31][32][33][34][35][36] follows first-order reversible kinetics. The rate of polymerization-precipitation is independent of the concentration of H + , and the reaction does not occur in the presence of oxidants [31].…”

“…These structural features explain the observed lubricity of poly-MTO. Understoichiometry with respect to the CH 3 /Re ratio of 4.6:5 and partial reduction by extra hydrogen equivalents are responsible for a high electric conductivity of poly-MTO [34,35]. Poly-MTO also contains amorphous areas with a defect stacking of double layers and with smaller content of water.…”

poly-methyltrioxorhenium{(CH3)0.92ReO3}Miller1, Scheidt2, Eickerling3 et al. 2006Phys. Rev. B41100View full textAdd to dashboardCite

“…8% of all Re atoms are lacking a methyl group) and acidic hydrogen atoms which formally act as a source of itinerant electrons of the transition-metal oxide lattice. 3 The results of band-structure calculations employing extended Hückel theory were interpreted by Genin et al 4 such that these demethylated Re atoms, which formally represent Re VI (d 1 ) sites, are effectively oxidized and their valence electrons are transferred to the band system. Only a minor part of these electrons (0.05% Re atoms 5 ) remains located at the metal sites which are in the following treated as Re(d 1 ) centers.…”

Organorhenium Oxides

“…9,10 Covalent perrhenates such as Me 3 SiOReO 3 and Me 3 SnOReO 3 are also suitable precursor compounds of R-ReO 3 complexes. 11 It has been shown that organozinc precursors are useful for the preparation of long-chain alkylrhenium oxides (2-14) 12 and σ-arylrhenium oxides (25-33) 13 while methyl-(1), alkenyl-(15-18, 22-24), and alkynyl-(19-21) rhenium(VII) oxides and nonperalkylated cyclopentadienylrhenium(VII) oxides (35,36) are available with organotin precursors. 14 Some derivatives such as (η 5cyclopentadienyl)trioxorhenium ( 35) and (η 1 -phenyl)trioxorhenium (25) are accessible by both methods.…”