A facile method is described for the synthesis of cationic Re(VII) cis oxo imido complexes of the form [Re(O)(NAr)(salpd)(+)] (salpd = N,N'-propane-1,3-diylbis(salicylideneimine)), 4, [Re(O)(NAr)(saldach)(+)] (saldach = N,N'-cyclohexane-1,3-diylbis(salicylideneimine)), 5, and [Re(O)(NAr)(hoz)(2)(+)] (hoz = 2-(2'-hydroxyphenyl)-2-oxazoline) (Ar = 2,4,6,-(Me)C6H2; 4-(OMe)C6H4; 4-(Me)C6H4; 4-(CF3)C6H4; 4-MeC6H4SO2), 6, from the reaction of oxorhenium(V) [(L)Re(O)(Solv)(+)] (1-3) and aryl azides under ambient conditions. Unlike previously reported cationic Re(VII) dioxo complexes, these cationic oxo imido complexes can be obtained on a preparative scale, and an X-ray crystal structure of [Re(O)(NMes)(saldach)(+)], 5a, has been obtained. Despite the multiple stereoisomers that could arise from tetradentate ligation of salen ligands to rhenium, one major isomer is observed and isolated in each instant. The electronic rationalization for stereoselectivity is discussed. Investigation of the mechanism suggests that the reactions of Re(V) with aryl azides proceed through an azido adduct similar to the group 5 complexes of Bergman and Cummins. Treatment of the cationic oxo imido complexes with a reductant (PAr3, PhSMe, or PhSH) results in oxygen atom transfer (OAT) and the formation of cationic Re(V) imido complexes. [(salpd)Re(NMes)(PPh3)(+)] (7) and [(hoz)(2)Re(NAr)(PPh3)(+)] (Ar = m-OMe phenyl) (9) have been isolated on a preparative scale and fully characterized including an X-ray single-crystal structure of 7. The kinetics of OAT, monitored by stopped-flow spectroscopy, has revealed rate saturation for substrate dependences. The different plateau values for different oxygen acceptors (Y) provide direct support for a previously suggested mechanism in which the reductant forms a prior-equilibrium adduct with the rhenium oxo (Re-VII = O <- Y). The second-order rate constants of OAT, which span more than 3 orders of magnitude for a given substrate, are significantly affected by the electronics of the imido ancillary ligand with electron-withdrawing imidos being most effective. However, the rate constant for the most active oxo imido rhenium(VII) is 2 orders of magnitude slower than that observed for the known cationic dioxo Re(VII) [(hoz)(2)Re(O)(2)(+)].