34248-12-9Relevant academic research and scientific papers
Mixed sugar-core-phosphate chelation of d-fructose 1,6-bisphosphate with the ReVO(tmen) metal fragment
Steinborn, Martin,Suhanji, Mihael,Kluefers, Peter
, p. 5749 - 5754 (2013)
Sugar phosphates provide metal-binding sites both at their sugar core and at their phosphate group(s). Mixed sugar-core-phosphate chelation has been considered as a typical bonding mode within the physiological pH range for the central metabolite d-fructose 1,6-bisphosphate. The ReVO(tmen) metal fragment was used to enrich this coordination type. The formation of the [ReO(tmen)(Fruf2,3H-21,6P2H2- κ3O2,3,P1)]- monoanion was determined by NMR spectroscopy and mass spectrometry. The model compound rac-glycerol 1-phosphate yielded similar results in terms of NMR spectroscopy. Crystal-structure analyses of [ReO(tmen)(rac-Glyc2,3H-21PH- κ3O2,3,P)]·2H2O and [ReO(phen)(rac-Glyc2,3H-21PH-κ3O2,3,P)] ·MeOH confirmed the coordination pattern.
Neutral '3 + 1' mixed-ligand oxorhenium(v) complexes with tridentate [S,N,S] chelates and aminoalkanethiols: Synthesis, characterization and structure determination
Triebe, Matthias,Spies, Hartmut,Seichter, Wilhelm,Leibnitz, Peter,Johannsen, Bernd
, p. 2471 - 2475 (2000)
'3 + l' Oxorhenium(v) complexes [ReO(SN(R')S)(SR)] (R' = Me, Et, Pr or Bu; SR = aminoalkane thiolate) have been synthesized by ligand exchange at www-trichloromonooxo-bis(triphenylphosphine)rhenium(v) with a mixture of HSN(R')SH and RSH in alkaline methanolic solution. The complexes were purified by column chromatography and characterized by elemental analysis, mass and IR spectroscopy and for selected compounds by 1H NMR spectroscopy. The structures of those complexes have been determined by X-ray diffraction analysis and revealed a change in the co-ordination geometry from square pyramidal to trigonal bipyramidal,: depending on the chelating (SN(R')S) moiety. The alkyl group (R1) was found to be arranged syn to the oxorhenium group. The Royal Society of Chemistry 2000.
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 (2008/10/09)
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
Synthesis and characterization of the (thiolato)rhenium(III) complexes trans-[Re(SR)2(R′2PCH2CH 2PR′2)2]+, where R is an alkyl, benzyl, or phenyl group and R′ is an ethyl or phenyl group. Single-crystal structural analyses of trans-[Re(SC6H5) ...
Chang, Lihsueh,Aizawa, Sen-Ichi,Heeg, Mary Jane,Deutsch, Edward
, p. 4920 - 4927 (2008/10/08)
Full title: Synthesis and characterization of the (thiolato)rhenium(III) complexes trans-[Re(SR)2(R′2PCH2CH 2PR′2)2]+, where R is an alkyl, benzyl, or phenyl group and R′ is an ethyl or phenyl group. Single-crystal structural analyses of trans-[Re(SC6H5)2(Et2PCH 2CH2PEt2)2]PF6, trans-[Re(SC6H4-p-CH3)2(Et 2PCH2CH2PEt2)2]PF 6, and trans-[Re(SC6H5)2(Ph2PCH 2CH2PPh2)2]CF3SO 3·1/2NCCH3. The mixed-ligand Re(III) complexes trans-[Re(SR)2(R′2PCH2CH 2PR′2)2]+ in which R′ = CH2CH3 (DEPE) and C6H5 (DPPE) while R = CH2CH3, CH2C6H4-p-OCH3, CH2C6H5, C6H4-p-CH3, C6H5, and C6H4-p-Cl have been synthesized and characterized. Preparation of these complexes proceeds from the Re(V) complexes trans-[Re(O)Cl3(PPh3)2] or trans-[ReO2Py4]Cl·2H2O utilizing excesses of thiol and phosphine as both reductants and ligands. The products are characterized by FAB mass spectroscopy, visible-UV spectroscopy, cyclic voltammetry, and elemental analyses. X-ray crystal structure analyses of prototypical complexes show that they have trans geometry. trans-[ReIII(SC6H5)2(DEPE) 2]PF6, chemical formula ReP5S2C32H58F6, crystallizes in the monoclinic space group P21/a, with Z = 2 and lattice parameters a = 15.6444 (9) A?, b = 13.932 (7) A?, c = 9.778 (3) A?, β = 110.91 (4)°, and V = 1990 (2) A?3. The final R1 value is 0.028. trans-[ReIII(SC6H4-p-CH3) 2(DEPE)2]PF6, chemical formula ReP5S2C34H62F6, crystallizes in the monoclinic space group P21/a, with Z = 2 and lattice parameters a = 11.729 (3) A?, b = 15.846 (2) A?, c = 12.254 (2) A?, β = 95.35 (2)°, V = 2267.5 (7) A?3. The final R1 value is 0.026. trans-[ReIII(SC6H5)2(DPPE) 2]-CF3SO3·1/2NCCH3, chemical formula ReP4S3F3O3N0.5C 66H59.5, crystallizes in the triclinic space group P1 with Z = 2 and lattice parameters a = 13.318 (4) A?, b = 13.341 (4) A?, c = 19.763 (5) A?, α = 77.82 (2)°, β = 72.55 (2)a?, γ = 66.02 (2)°, V = 3044 (1) A?3. The final R1 value is 0.043. For all three complexes the Re-S bond lengths are similar (2.303, 2.305, and 2.321 A?) with the longest bond length associated with the more electron-donating p-tolulenethiolato ligand. Likewise, the Re-P distances are similar (2.45, 2.45, and 2.47 A?), with the longest bond length associated with the more sterically demanding DPPE ligand. These Re(III)-S and Re(III)-P bond lengths are nearly identical to the corresponding Tc(III) bond lengths. The potentials of the reversible Re(III/II) couples depend on the properties of the thiolato and diphosphine ligands and are ca. 0.3 V more negative than those of the analogous Tc(III/II) couples.
