Synthesis and Characterization of Unusual Oxidorhenium(V) Cores

Abstract

Reactions of (NBu4)[ReOCl4] with N‐(N″,N″‐dialkylaminothiocarbonyl)‐N′‐(2‐hydroxyphenyl)benzamidines (H2L1) give complexes of the compositions [ReOCl(L1)] (1), cis‐[ReO(L1)(OMe)] (2), or cis,cis‐[{ReO(L1)}2O] (3) depending on the conditions applied. Compound 3 contains a bridging oxygen atom in the cis position to the terminal oxido ligands of both rhenium atoms. The analogous dimeric, sulfur‐bridged compound [{ReO(L1)}2S] (4) was obtained by the reaction of 1 with Na2S.

Rules of Boron–Nitrogen Doping in Defect Graphene Sheets: A First‐Principles Investigation of Band‐Gap Tuning and Oxygen Reduction Reaction Catalysis Capabilities

“…Usually, however, the linear {O=Re–O–Re=O} 4+ ( trans, trans ) core is formed with some electron transfer to the oxido bridge. Only some rare cases are known with cis , cis or cis , trans coordination of terminal and bridging oxido ligands 20. In the present case, the common trans , trans conformation is most probably inhibited by the preferred formation of the building block around the rhenium atom Re2.…”

Syntheses and Structures of Nitridorhenium(V) and Nitridotechnetium(V) Complexes with N,N‐[(Dialkylamino)(thiocarbonyl)]‐N′‐(2‐hydroxyphenyl)benzamidines

“…This bond length equalization is evenextended to the C2–N6 bonds, which are significantly shorter than expected for single bonds. All the M ‐O, M ‐N and M –S bonds are slightly longer than those in the corresponding oxo complexes 2,5. This can be understood by the larger steric bulk of the M ≡N triple bond, which results in larger N≡ M ‐ X (equatorial) angles and consequently in a somewhat less effective overlap between the ligand and the d orbitals of the metal ions.…”

“…Most of the isolated complexes with these ligands have oxorhenium(V) or oxotechnetium(V) cores. Five‐coordinate oxorhenium(V) and oxotechnetium (V) complexes,2 as well as cis methoxo compounds,5 ‘3+2’ mixed‐ligand complexes,6 and dimeric oxorhenium(V) complexes5 were isolated and structurally characterized. Only one exceptional compound is an octahedral technetium(III) complex 2.…”