Solvation structure of lanthanide(iii) ions in solvent mixtures of N,N-dimethylformamide and N,N-dimethylacetamide studied by titration Raman spectroscopyElectronic supplementary information (ESI) available: Crystallographic data (single crystal, [Gd(DMF)4(DMA)4](ClO4)3), (CCDC reference number 185878). See http://www.rsc.org/suppdata/cp/b2/b204162f/

Umebayashi, Yasuhiro; Matsumoto, Kimihisa; Mekata, Isamu; Ishiguro, Shin‐ichi

doi:10.1039/b204162f

Cited by 28 publications

(8 citation statements)

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“…[23][24][25][26][27] Solvation steric effect also modifies an aspect of preferential solvation (sterically controlled preferential solVation) of a metal ion in solvent mixtures. [28][29][30][31][32] According to our Raman spectroscopic study, 31,32 N,Ndimethylpropionamide (DMPA) exists as either planar cis or nonplanar staggered conformer in the bulk, as shown in Chart 1, and the former is enthalpically more favorable by ca. 5 kJ mol -1 than the latter.…”

Section: Introductionmentioning

confidence: 99%

Conformation of Solvent N,N-Dimethylpropionamide in the Coordination Sphere of the Zinc(II) Ion Studied by Raman Spectroscopy and DFT Calculations

et al. 2005

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Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion.

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Section: Introductionmentioning

confidence: 99%

Conformation of Solvent N,N-Dimethylpropionamide in the Coordination Sphere of the Zinc(II) Ion Studied by Raman Spectroscopy and DFT Calculations

et al. 2005

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“…10 Crystal structures of the metal solvate ions have been determined for various amides as solvent, and it is indicated that the M-O-C and dihedral M-O-C-N angles are distorted from those of usual six-coordination. [11][12][13] It is also indicated that the intra-molecular geometry of amides is appreciably distorted upon coordination to the metal ion. These suggest that solvent molecules alleviate solvation steric effect upon coordination to the metal ion by changing both their mutual orientation and intra-molecular geometry.…”

Section: Introductionmentioning

confidence: 99%

Conformational equilibria of solvent N,N-dimethylpropionamide in the bulk and in the coordination sphere of the manganese(ii) ionElectronic supplementary information (ESI) available: non-planar staggered and planar cis Gaussian results. See http://www.rsc.org/suppdata/cp/b3/b302143b/

Umebayashi

Matsumoto

Mune

et al. 2003

Phys. Chem. Chem. Phys.

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“…6, together with the total solvation number nT = nDMF + nDMA. 34 As seen, the total solvation number of Nd 3+ remains practically eight over the range 0 < xDMA < 0.8, then slightly decreases. A similar variation is seen also for Gd 3+ , though the decrease starts at a slightly earlier stage of xDMA than that for Nd 3+ .…”

Section: +mentioning

confidence: 70%

Characterization of Metal Ions in Coordinating Solvent Mixtures by Means of Raman Spectroscopy

2004

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Neat DMF and DMA show the in-plane bending δ(O=C-N) vibration at 660 cm -1 and the symmetric stretching ν(N-CH3) vibration at 740 cm -1 , respectively. The metal(II) perchlorate solution usually shows a shoulder band at a higher frequency region of the free solvent band, which is ascribed to the bound Titration Raman spectroscopy has been developed for studying the solvation structure of metal ions in solution. The method affords us the solvation number, and the value thus obtained in neat solvents is in good agreement with that determined by EXAFS. The method is then applied to solvent mixtures, and the individual solvation number for each solvent is extracted. In a solvent mixture of N,N-dimethylformamide (DMF) and N,N,N′,N′-tetramethylurea (TMU), the metal ion prefers DMF to TMU, which is ascribed to the solvation steric effect. The same applies also for the solvent mixture of N,N-dimethylpropionamide (DMPA) and DMF. However, unlike TMU, DMPA changes its conformation from the planar cis to non-planar staggered upon solvation to the metal ion. The enthalpy for the conformational change of DMPA is positive in the bulk, while it is significantly negative in the coordination sphere of the manganese(II) ion. Here, we briefly describe the procedure of measurements and analyses for the titration Raman spectroscopy, and review the solvation structure of the alkaline earth, first transition metal(II) and lanthanide(III) ions in some solvent mixtures in view of solvation steric effect.

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Cited by 28 publications

References 20 publications

Conformation of Solvent N,N-Dimethylpropionamide in the Coordination Sphere of the Zinc(II) Ion Studied by Raman Spectroscopy and DFT Calculations

Conformation of Solvent N,N-Dimethylpropionamide in the Coordination Sphere of the Zinc(II) Ion Studied by Raman Spectroscopy and DFT Calculations

Conformational equilibria of solvent N,N-dimethylpropionamide in the bulk and in the coordination sphere of the manganese(ii) ionElectronic supplementary information (ESI) available: non-planar staggered and planar cis Gaussian results. See http://www.rsc.org/suppdata/cp/b3/b302143b/

Characterization of Metal Ions in Coordinating Solvent Mixtures by Means of Raman Spectroscopy

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