14405-69-7Relevant academic research and scientific papers
Solid state study on rhenium dimethylphosphinoethane complexes: X-ray crystal structures of trans-[ReO2 (dmpe)2]PF 6·2H2O, trans-[ReO(OH)(dmpe)2](CF 3SO3)2, trans-[ReN(Cl)(dmpe) 2]CF3SO3 and trans-[ReCl2(dmpe) 2]ReO4
Engelbrecht,Jurisson,Cutler,Den Drijver,Roodt
, p. 83 - 99 (2005)
The reaction of trans-[ReO2(en)2]Cl with dimethylphosphinoethane (dmpe) yielded the yellow complex trans-[ReO2 (dmpe)2]Cl (1), which, upon reaction with CF3SO 3H, yields orange crystals of the oxo-hydroxo complex trans-[ReO (OH)(dmpe)2](CF3SO3)2 (2). Reaction of trans-[ReNCl2(PPh3)2] with dmpe resulted in orange crystals of trans-[ReN(Cl)(dmpe)2]-CF3SO 3 (3). Adjustment of the pH of a solution of trans-[ReN(Cl)(dmpe) 2]CF3SO3 to 11.7 with NaOH resulted in the formation of yellow crystals of trans-[ReCl2(dmpe) 2]ReO4 (4). A shortening of the Re-P bond distances were observed as the axial ligands (i.e., core: O=ReV-OH V=O V-Cl III-Cl) increased the electron density on the metal center, allowing for better Re-P π back bonding. The preliminary pKa determination for the protonation of [ReO2(dmpe)2]+ to form [ReO(OH)(dmpe)2]2+ showed the pKa2 to be 2(dmpe)2]+: monoclinic space group P21/c with a = 11.5299(7) A, b = 15.2397(9) A, c = 15.0230(9) A, β = 97.7260(10)°, Z = 4; trans-[ReO(OH)(dmpe)2]2+: monoclinic space group P2 1/c with a = 8.0426(4) A, b = 11.5472(6) A, c = 16.0303(8) A, β = 101.9360(10)°, Z = 2; trans-[ReN(Cl) (dmpe)2]+: orthorhombic space group Pmc21 with a = 11.5068(10) A, b = 9.6656(8) A, c = 12.1772(11) A, Z = 2; trans-[Re(Cl)2(dmpe)2]+: monoclinic space group P21/c with a = 19.375(3) A, b = 8.6840(12) A, c = 15.910(2) A, β = 111.270(3)°, Z = 4. The conformation of the two dmpe ligands in all of the complexes described were λδ (eclipsed). Copyright
Coupled electronic states in trans-Dioxo complexes of rhenium(V) and osmium(VI) probed by near-infrared and visible luminescence spectroscopy
Savoie, Carole,Reber, Christian
, p. 844 - 852 (2007/10/03)
trans-Dioxo complexes of rhenium(V) and osmium(VI) with ethylenediamine imidazole, and oxalate ancillary ligands show luminescence maxima varying between 620 and 900 nm. The resolved vibronic progressions of the rhenium complexes have intensity distributions that cannot be rationalized with harmonic potential energy surfaces. The broadband spectra of the osmium(VI) complexes also show deviations from the band shapes expected for a harmonic ground-state potential surface. We use the large variation of luminescence energies and the vibronic features to show the influence of excited electronic states on the ground-state potential energy surface. The vibronic structure and band envelopes of the luminescence spectra are calculated using the lowest energy adiabatic surface obtained from three interacting electronic states.
Formation of the trans-[ReO2]+ 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) ...
Luna, Silvio Alvarez,Bolzati, Cristina,Duatti, Adriano,Zucchini, Gian Luigi,Bandoli, Giuliano,Refosco, Fiorenzo
, p. 2595 - 2598 (2008/10/08)
Full title: Formation of the trans-[ReO2]+ 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). 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-dioxorhenium(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 counterfoils (ReO4-, Cl-, PF6-). The perrhenate and chloride salts, 4(ReO4) and 4(Cl), 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 P1 with cell parameters a = 5.533 (1) ?, b = 11.899 (3) ?, c = 13.622 (3) ?, V = 853.2 (4) ?3, Z = 2, R = 0.063, and Rw = 0.081 for 3006 observed reflections.
