Multiple bonds between main-group elements and transition metals: CXXXI. Allyl-, vinyl- and related rhenium(VII) trioxides: synthesis and degradation

Abstract The preparations are described of the unstable allyl-, pseudo-allyl- and benzyl- complexes of formula RReO 3 (R = C 3 H 5 -, CH 2 CMeCH − , CH 2 CHCHCHCH 2 − , C 2 H 5 OC(O)CH 2 − , PhCH 2 − from Re 2 O 7 and the tin reagents RSn( n -Bu) 3 . In situ -NMR studies show that the allylic species exhibit η 1 -coordination. The vinyl analogue (CH 2 CMe)ReO 3 is prepared from Re 2 O 7 and Zn(CMeCH 2 ) 2 . Quinuclidine adducts of type RReO 3 · Quin are also reported. Decomposition studies of the allyl and 1-methallyl derivatives show concentration-dependent radical pathways in anhydrous solution (1,5-hexadiene and propene evolution) and facile hydrolysis (propene evolution) at low temperature. Allyltrioxorhenium(VII) does not react with oxygen, while peroxides predominantly yield 2-propen-1-ol.