Synthesis and Characterization of Mixed-Ligand Oxorhenium Complexes with the SNN Type of Ligand. Isolation of a Novel ReO[SN][S][S] Complex

A, Rey; Pirmettis, Ioannis; Pelecanou, Maria; Papadopoulos, Minas; Raptopoulou, Catherine P.; Mallo, L.; Ci, Stassinopoulou; Terzis, Aris; Chiotellis, E.; León, A.

doi:10.1021/ic991491v

Cited by 16 publications

(14 citation statements)

References 42 publications

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“…, there is little difference between the Re-X bond lengths and O=Re-X bond angles of trans-ReO(SH) 2 (NH 2 )(NH 3 ) optimized at the PBE0/6-31G(d,p):LANL2TZ and PBE0/cc-pVDZ-(pp) levels of calculation. Also, the Re-X bond lengths and O=Re-X bond angles in the calculated equilibrium structures generally lie within the ranges observed from crystallographic studies of typical ReO-N 2 S 2 and -NS 3 complexes[30][31][32]. Similar results were observed for…”

supporting

confidence: 84%

Using potential energy surface scans to examine the bond dissociation energies of trans-ReOS2N2 and [ReOS3N]1− model complexes

Kreuer

Demoin

et al. 2014

Computational and Theoretical Chemistry

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Developing Re(V)-based therapeutic agents, where the ReO 3+ core is coordinated to a multidentate ligand, is of interest in the radiopharmaceutical sciences because of the desirable nuclear properties of 186 Re/ 188 Re. A reliable yet cost-effective computational method for evaluating the strength of each coordination bond while preserving the integrity of the metal-ligand complex would provide quantitative input for ligand design. A relaxed potential energy surface (PES) scan approach is assessed for trans-ReO(SH) 2 (NH 2)(NH 3), [ReO(SH) 3 (NH 2)] 1-, and [ReO(SH) 3 (N(H)CHO)] 1model complexes to calculate bond dissociation energies (BDEs) for Re-NH 3 , Re-NH 2 , Re-N(H)CHO and Re-SH bonds, common components of Re(V) coordination environments. The PES scans were performed using various combinations of DFT/coupled-cluster methods and basis sets, and the effect of bulk solvent was examined by using the integral equation formalism of the polarizable continuum model (IEF-PCM). BDEs obtained from the PES scans are compared to those obtained for infinite separation. In the gas phase, the BDE curves reach about 90% of the total BDE at 2 Å and plateau by 3.0 to 3.5 Å beyond the equilibrium bond length; in the presence of implicit solvent, the BDE water curves plateau at a shorter distance and more than 90% of the total BDE is recovered at 2 Å. The gas-phase PES scans follow the desired reaction coordinate for NH 3 , [N(H)CHO] 1and SH 1-, but not for the poor leaving group NH 2 1-. The desired heterolytic cleavage of the Re-NH 2 bond is achieved when the PES scans are performed in the presence of solvent. Elongating the Re-S/N bonds in a rigid, multidentate trans-ReO-N 2 S 2 complex yields BDE trends similar to those found for the model complexes (Re-NH 2 > Re-N(H)CHO > Re-SH > Re-NH 3).

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supporting

confidence: 84%

Using potential energy surface scans to examine the bond dissociation energies of trans-ReOS2N2 and [ReOS3N]1− model complexes

Kreuer

Demoin

et al. 2014

Computational and Theoretical Chemistry

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“…, in order to introduce a stereogenic center upon complexation of rhenium. It should be noted that some unsymmetrical NSS nitrogen ligands are also reported 61 but we avoided nitrogen for spectroscopic reasons (quadrupolar coupling). We started with the synthesis of the tridentate ligand 2-(2-mercaptoethylthio)ethanol and the formation of rhenium complex 2, but the complexes were found to be unstable over silica gel and consequently could not be obtained in chemically pure form.…”

Section: A Experimental Resultsmentioning

confidence: 99%

“…It is already known that the protons which are directed towards the oxygen atom (H endo ) are downshielded compared to the H exo due to the anisotropy of the ReQO double bond. 61,71 All protons are magnetically non-equivalent, giving rise to couplings between each of them (see Fig. 2).…”

Section: B Nmr Spectramentioning

confidence: 99%

“…Up to now, many ''3 + 1'' oxorhenium(V) and oxotechnetium(V) complexes have been synthesized with various tridentate and monodentate ligands as potential candidates for new radiopharmaceuticals. 56 This approach was mainly developed by the groups of Spies, [57][58][59][60] Chiotellis, [60][61][62][63] and Zubieta. 64,65 The ''3 + 1'' oxorhenium(V) structure enables the design of very simple molecules with a stereogenic rhenium center (see Fig.…”

Section: Introductionmentioning

confidence: 99%

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Chiral oxorhenium(v) complexes as candidates for the experimental observation of molecular parity violation: a structural, synthetic and theoretical study

Montigny

Bast

Gomes

et al. 2010

Phys. Chem. Chem. Phys.

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We report the synthesis and resolution of a series of new chiral "3 + 1" oxorhenium(V) complexes, designed for high-resolution laser spectroscopy experiments probing molecular parity-violation (PV) effects in the Re=O stretching mode frequency. These complexes display a particularly simple chemical structure, with the rhenium atom as the stereogenic center, and show large PV energy differences according to our calculations. They were obtained in the racemic and enantioenriched forms, in the latter case by using either semi-preparative chiral HPLC resolution or enantioselective synthesis. The vibrational transition frequency differences between the enantiomeric pairs due to PV have been calculated with two- and four-component relativistic Hamiltonians using Hartree-Fock (HF) and density functional theory (DFT). For three complexes, including one synthesized in enantioenriched form, our HF calculations predict frequency differences above the present resolution limit of 1 Hz. These results confirm the order of magnitude for the calculated HF PV vibrational frequency differences reported earlier for this class of compounds [P. Schwerdtfeger and R. Bast, J. Am. Chem. Soc., 2004, 126, 1652]. However, at the DFT level the PV vibrational frequency differences are in some cases reduced by an order of magnitude, but are still within the sensitivity of 0.01 Hz, which is the anticipated sensitivity in a new proposed experiment. We therefore believe that the present study represents an important step towards the experimental observation of PV in molecular systems, and emphasizes the extreme sensitivity of the PV vibrational frequency difference to the chemical environment around the rhenium center.

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“…In both compounds the coordination geometry around the five-coordinate Re v atom is best described as distorted square-pyramidal, with the axial ReϪO(1) bond length significantly shorter than the ReϪL(basal) distances. The ReϭO (1) ReϪO (1) 1.683 (8) 1.673 (5) ReϪS (1) 2.285 (3) 2.290(2) ReϪS (2) 2.367 (3) 2.364(2) ReϪS (3) 2.285 (3) 2.282(2) ReϪS (4) 2.327 (3) 2.345(2) S(4)ϪC (5) 1.745 (13) 1.734 (7) (3) 130.35 (14) 127.86 (7) S(3)ϪReϪS (4) 87.64 (12) 88.29(7) S(1)ϪReϪS (4) 82.38 (12) 81.15(7) S(3)ϪReϪS (2) 84.25 (11) 84.44(7) S(1)ϪReϪS (2) 84.18 (11) 84.76(7) S(4)ϪReϪS (2) 154.00 (11) 155.29(7) ReϪS(4)ϪC (5) 110.7(4) 110.1 (2) 3ϩ1 compounds. [1Ϫ6,12Ϫ16] The CϪS bond lengths [1.745(13) Å (1), 1.734(7) Å (2)] are comparable and are similar to those found previously, [17] which range from 1.68 to 1.73 Å .…”

Section: Crystal Structures Of [Re(o)(κ 3 -Sss)(κ 1 -Simz)] (1) and [mentioning

confidence: 99%

New Mixed-Ligand ReV Complexes with Bis(2-mercaptoethyl) Sulfide and Functionalized Thioimidazolyl Ligands

Palma¹,

Correia²,

Domingos³

et al. 2002

Eur. J. Inorg. Chem.

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The preparation of the mixed‐ligand ReV complexes [Re(O)(κ3‐SSS)(κ1‐Simz)] (1), [Re(O)(κ3‐SSS)(κ1‐Simz)]·HCl (2) and [Re(O)(κ3‐SSS)(κ1‐SimzCOGlyGly)] (3) are described. These [3+1] type compounds are stabilized by tridentate bis(2‐mercaptoethyl) sulfide (HSSSH) and by monodentate functionalized thioimidazolyl ligands. Complexes 1, 2 and 3 were fully characterized by IR and 1H NMR spectroscopy, and by X‐ray diffraction analysis in the case of 1 and 2. In complexes 1 and 2 the Re atom is five‐coordinate, presenting a distorted square pyramidal coordination geometry. Based on the angular structural parameter, τ, this distortion lies towards a trigonal bipyramidal geometry (τ = 0.40, 1; τ = 0.46, 2). (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Synthesis and Characterization of Mixed-Ligand Oxorhenium Complexes with the SNN Type of Ligand. Isolation of a Novel ReO[SN][S][S] Complex

Cited by 16 publications

References 42 publications

Using potential energy surface scans to examine the bond dissociation energies of trans-ReOS2N2 and [ReOS3N]1− model complexes

Using potential energy surface scans to examine the bond dissociation energies of trans-ReOS2N2 and [ReOS3N]1− model complexes

Chiral oxorhenium(v) complexes as candidates for the experimental observation of molecular parity violation: a structural, synthetic and theoretical study

New Mixed-Ligand ReV Complexes with Bis(2-mercaptoethyl) Sulfide and Functionalized Thioimidazolyl Ligands

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