The complexes ReNCl2(PPh3)2 (1), ReCl4(PPh3)2 (2), and ReCl3(CH3CN)(PPh3)2 (3) react with bidentate (L2) and tetradentate (L1) chelating amines and with 1, 4, 8, 11-tetraazacyclotetradecane (cyclam) at room temperature, to afford cationic trans-di-oxorhenium(V) complexes of the type [ReO2(Ln)n]+ (n = 1, 2) and [ReO2(cyclam)]+ (4). These reactions constitute an unexpected alternative route to the synthesis of rhenium(V) complexes containing the trans-[ReO2]+ group. The complex cation 4 was isolated with three different counterions (ReO4-, Cl-, PF6-6). The perrhenate and chloride salts, 4(ReO4) and 4(C1), show a single infrared absorption at 772 cm-1, assigned to the asymmetric stretching vibration of the trans-[ReO2]+ group, while the hexafluorophosphate salt, 4(PF6), shows two absorptions at 809 and 776 cm-1, assigned to the same vibration. This fact has been attributed to the presence of two symmetry-inequivalent molecules of the cation 4 in the solid-state structure of 4(PF6), which has been determined by X-ray crystallography. Complex cation 4 is monomeric and has an approximately octahedral arrangement of ligands around the rhenium atom. The crystal structure consists of two independent cations and anions, and each ion has a crystallographically imposed symmetry center. 4(PF6) crystallizes in the triclinic space group Pi with cell parameters a = 5.533 (1) Å, 3= 11.899 (3) Å, c = 13.622 (3) Å, V = 853.2 (4) Å3, Z = 2, R = 0.063, and Rw = 0.081 for 3006 observed reflections. © 1992, American Chemical Society. All rights reserved.
Formation of the Trans-[Re(O2)]+ Group from the Reactions of ReNCl2(PPh3)2, ReCl4(PPh3)2, and ReCl3(CH3CN)(PPh3)2 with Chelating Amines and Tetraazamacrocycles. Crystal Structure Of Trans-[ReO2(Cyclam)](PF6) (Cyclam = 1, 4, 8, 11-Tetraazacyclotetradecane)
DUATTI, Adriano;
1992
Abstract
The complexes ReNCl2(PPh3)2 (1), ReCl4(PPh3)2 (2), and ReCl3(CH3CN)(PPh3)2 (3) react with bidentate (L2) and tetradentate (L1) chelating amines and with 1, 4, 8, 11-tetraazacyclotetradecane (cyclam) at room temperature, to afford cationic trans-di-oxorhenium(V) complexes of the type [ReO2(Ln)n]+ (n = 1, 2) and [ReO2(cyclam)]+ (4). These reactions constitute an unexpected alternative route to the synthesis of rhenium(V) complexes containing the trans-[ReO2]+ group. The complex cation 4 was isolated with three different counterions (ReO4-, Cl-, PF6-6). The perrhenate and chloride salts, 4(ReO4) and 4(C1), show a single infrared absorption at 772 cm-1, assigned to the asymmetric stretching vibration of the trans-[ReO2]+ group, while the hexafluorophosphate salt, 4(PF6), shows two absorptions at 809 and 776 cm-1, assigned to the same vibration. This fact has been attributed to the presence of two symmetry-inequivalent molecules of the cation 4 in the solid-state structure of 4(PF6), which has been determined by X-ray crystallography. Complex cation 4 is monomeric and has an approximately octahedral arrangement of ligands around the rhenium atom. The crystal structure consists of two independent cations and anions, and each ion has a crystallographically imposed symmetry center. 4(PF6) crystallizes in the triclinic space group Pi with cell parameters a = 5.533 (1) Å, 3= 11.899 (3) Å, c = 13.622 (3) Å, V = 853.2 (4) Å3, Z = 2, R = 0.063, and Rw = 0.081 for 3006 observed reflections. © 1992, American Chemical Society. All rights reserved.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
