Precise structural characterizations of the hexaaquovanadium(III) and diaquohydrogen ions. X-ray and neutron diffraction studies of [V(H2O)6][H5O2](CF3SO3)4

Cotton, F. Albert; Fair, C. K.; Lewis, GE; Mott, Graham N.; Ross, F. K.; Schultz, Arthur J.; Williams, Jack M.

doi:10.1021/ja00330a047

Cited by 68 publications

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“…As discussed in detail by Cotton et al, 33 The extent of deviation from T h symmetry is measured with the twist angle φ that is defined as the dihedral angle between the plane of a water molecule and the closer MO 4 plane that includes its oxygen atom. The sign of φ is referred to the C 3 axis of the MO 6 octahedron that corresponds to the symmetry axis of the D 3d structures.…”

Section: Resultsmentioning

confidence: 99%

Electronic Structure of 3d [M(H₂O)₆]³⁺ Ions from Sc^III to Fe^III: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Kallies

Meier

2001

Inorg. Chem.

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The metal-donor atom bonding along the series of 3d[M(H2O)6](3+) ions from Sc(3+) to Fe(3+) has been investigated by density-functional calculations combined with natural localized bond orbital analyses. The M-OH(2) bonds were considered as donor-acceptor bonds, and the contributions coming from the metal ion's 3d sigma-, 3d pi-, and 4s sigma-interactions were treated individually. In this way, the total amount of charge transferred from the water oxygen-donor atoms toward the appropriate metal orbitals could be analyzed in a straightforward manner. One result obtained along these lines is that the overall extent of ligand-to-metal charge transfer shows a strong correlation to the hydration enthalpies of the aqua metal ions. If the contributions to the total ligand-to-metal ion charge transfer are divided into sigma- and pi-contributions, it turns out that Cr(3+) is the best sigma-acceptor, but its pi-accepting abilities are the weakest along the series. Fe(3+) is found to be the best pi-acceptor among the 3d hexaaqua ions studied. Its aptitude to accept sigma-electron density is the second weakest along the series and only slightly higher than that of Sc(3+) (the least sigma-acceptor of all ions) because of the larger involvement of the Fe(3+) 4s orbital in sigma-bonding. The strengths of the three types of bonding interactions have been correlated with the electron affinities of the different metal orbitals. Deviations from the regular trends of electron affinities along the series were found for those [M(H2O)6](3+) ions that are subject to Jahn-Teller distortions. In these cases (d(1) = [Ti(H2O)6](3+), d(2) = [V(H2O)6](3+), and d(4) = [Mn(H2O)6](3+)), ligand-to-metal charge transfer is prevented to go into those metal orbitals that contain unpaired d electrons. A lowering of the complex symmetry is observed and coupled with the following variations: The Ti(3+)- and V(3+)-hexaaqua ions switch from T(h)() to C(i)() symmetry while the Mn(3+)-hexaaqua ion moves to D(2)(h)() symmetry. The loss of orbital overlap leading to a diminished ligand-to-metal charge transfer toward the single occupied metal orbitals is compensated by amplified bonding interactions of the ligand orbitals with the unoccupied metal orbitals to some extent.

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Section: Resultsmentioning

confidence: 99%

Electronic Structure of 3d [M(H₂O)₆]³⁺ Ions from Sc^III to Fe^III: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Kallies

Meier

2001

Inorg. Chem.

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“…The V m, Cr m, Mn In, Fein and Coin hexaaqua ions, for example, have all been structurally characterized as the alums Cs[M(H20)6](SOa)2.6H20 (Beattie, Best, Skelton & White, 1981), as has that of Ti m (Sygusch, 1974). However, full structural data for only one first-row transition metal ion, Vin (Cotton, Fair, Lewis, Mott, Ross, Schultz & Williams, 1984), and one second-row transition metal ion, Ru m (Bernhard, Btirgi, Hauser, Lehmann & Ludi, 1982), forming [M(H20)6]X3 complexes have been reported. The p-toluenesulfonate anion (pts-) has proved successful in the past in crystallizing hexaaqua ions such as those of Ru n and Ru In (Bernhard et al, 1982), Cu n (Couldwell, Prout, Robey, Taylor & Rossotti, 1978) and Zn n (Hargreaves, 1957).…”

Section: Commentmentioning

confidence: 99%

“…Bond lengths and angles within the cations are unexceptional, with a small range of Ti---O distances [2.018 (5)-2.046 (6)/~], similar to the lengths observed for the caesium titanium alum (Sygusch, 1974). The Ti----O bonds are longer than the V---O bonds in the corresponding cation, where the mean distance is 1.995/~, (Cotton et al, 1984). A decrease in the MIn--O distance such as this is expected on changing the configuration of the central metal ion from d 1 to d 2 (Cotton & Wilkinson, 1988).…”

Section: Me 3 (I)mentioning

confidence: 99%

Hexaaquatitanium(III) Tris(p-Toluenesulfonate) Trihydrate

Aquino¹,

Clegg²,

Liu³

et al. 1995

Acta Crystallogr C

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“…The proton-assisted H-bonds (OÁ Á ÁH + Á Á ÁO, 2.3-2.5 Å ) are markedly shorter than normal O-HÁ Á ÁO bond. Therefore, the OÁ Á ÁO separations can be conveniently used as a probe to determine the location of the protons [21,22]. In the present case, the OÁ Á ÁO distances around O8wA(B) (ÀO5w, 2.394(2.405), ÀO4w, 2.588(2.414), ÀO2w, 2.622(2.616) Å ) are remarkably shorter than the remaining ones Fig.…”

mentioning

confidence: 73%

Unprecedented 2-D hydrated proton encapsulated in supramolecular framework built of [Mo3O4(C2O4)(H2O)3]2−

Zhao

2008

Inorganic Chemistry Communications

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Precise structural characterizations of the hexaaquovanadium(III) and diaquohydrogen ions. X-ray and neutron diffraction studies of [V(H2O)6][H5O2](CF3SO3)4

Cited by 68 publications

References 0 publications

Electronic Structure of 3d [M(H₂O)₆]³⁺ Ions from Sc^III to Fe^III: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Electronic Structure of 3d [M(H₂O)₆]³⁺ Ions from Sc^III to Fe^III: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Hexaaquatitanium(III) Tris(p-Toluenesulfonate) Trihydrate

Unprecedented 2-D hydrated proton encapsulated in supramolecular framework built of [Mo3O4(C2O4)(H2O)3]2−

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Precise structural characterizations of the hexaaquovanadium(III) and diaquohydrogen ions. X-ray and neutron diffraction studies of [V(H2O)6][H5O2](CF3SO3)4

Cited by 68 publications

References 0 publications

Electronic Structure of 3d [M(H2O)6]3+ Ions from ScIII to FeIII: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Electronic Structure of 3d [M(H2O)6]3+ Ions from ScIII to FeIII: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Hexaaquatitanium(III) Tris(p-Toluenesulfonate) Trihydrate

Unprecedented 2-D hydrated proton encapsulated in supramolecular framework built of [Mo3O4(C2O4)(H2O)3]2−

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Electronic Structure of 3d [M(H₂O)₆]³⁺ Ions from Sc^III to Fe^III: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses

Electronic Structure of 3d [M(H₂O)₆]³⁺ Ions from Sc^III to Fe^III: A Quantum Mechanical Study Based on DFT Computations and Natural Bond Orbital Analyses