Formation and Solid State Structures of Highly Crystalline Guanidinium Salts of Sulfonated Tertiary Phosphanes

Kathó, Ágnes; Bényei, Attila; Joó, Ferenc; Sági, Maria

doi:10.1002/1615-4169(200206)344:3/4<278::aid-adsc278>3.0.co;2-c

Cited by 15 publications

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“…Recently we managed to determine [9] the structure of cesium salt of (4-diphenylphosphino)benzenesulfonic acid and it contained water molecule in the lattice, too. A real breakthrough could be reached by applying the Ward [10]-Kathó [11] approach to utilize strong hydrogen donor cations especially gua + to stabilize the crystal lattice of sulfonated phosphanes and five new structures of various sulfonated phosphans have been published. By this method we managed to crystallize 2, too.…”

Section: Resultsmentioning

confidence: 99%

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

Bényei

Gulyás²,

Ozawa

et al. 2007

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 99%

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

Bényei

Gulyás²,

Ozawa

et al. 2007

Journal of Organometallic Chemistry

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“…Thus, we used the guanidine cation, which is known to aid the preparation of single crystals due to its strong ability to form hydrogen bonds. 31 Single crystals of {C(NH 2 ) 3 }[Tl(dota)]•H 2 O could be grown at the interface between 96% ethanol and a solution prepared by method (c) described above.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

[Tl^III(dota)]⁻: An Extraordinarily Robust Macrocyclic Complex

Fodor¹,

Bányai²,

Bényei³

et al. 2015

Inorg. Chem.

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The X-ray structure of {C(NH2)3}[Tl(dota)]·H2O shows that the Tl(3+) ion is deeply buried in the macrocyclic cavity of the dota(4-) ligand (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate) with average Tl-N and Tl-O distances of 2.464 and 2.365 Å, respectively. The metal ion is directly coordinated to the eight donor atoms of the ligand, which results in a twisted square antiprismatic (TSAP') coordination around Tl(3+). A multinuclear (1)H, (13)C, and (205)Tl NMR study combined with DFT calculations confirmed the TSAP' structure of the complex in aqueous solution, which exists as the Λ(λλλλ)/Δ(δδδδ) enantiomeric pair. (205)Tl NMR spectroscopy allowed the protonation constant associated with the protonation of the complex according to [Tl(dota)](-) + H(+) ⇆ [Tl(Hdota)] to be determined, which turned out to be pK(H)Tl(dota) = 1.4 ± 0.1. [Tl(dota)](-) does not react with Br(-), even when using an excess of the anion, but it forms a weak mixed complex with cyanide, [Tl(dota)](-) + CN(-) ⇆ [Tl(dota)(CN)](2-), with an equilibrium constant of Kmix = 6.0 ± 0.8. The dissociation of the [Tl(dota)](-) complex was determined by UV-vis spectrophotometry under acidic conditions using a large excess of Br(-), and it was found to follow proton-assisted kinetics and to take place very slowly (∼10 days), even in 1 M HClO4, with the estimated half-life of the process being in the 10(9) h range at neutral pH. The solution dynamics of [Tl(dota)](-) were investigated using (13)C NMR spectroscopy and DFT calculations. The (13)C NMR spectra recorded at low temperature (272 K) point to C4 symmetry of the complex in solution, which averages to C4v as the temperature increases. This dynamic behavior was attributed to the Λ(λλλλ) ↔ Δ(δδδδ) enantiomerization process, which involves both the inversion of the macrocyclic unit and the rotation of the pendant arms. According to our calculations, the arm-rotation process limits the Λ(λλλλ) ↔ Δ(δδδδ) interconversion.

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“…It is important to indicate that the corresponding interatomic distances O(3) … O(39) and O(3) … C (10) are very close to each other and equal to 3.0273(4) and 3.0201(4) A ˚, respectively. For comparison, the O … C separation in the crystal of tetrakis(guanidinium) tris(3-sulfonatophenyl)phosphine nitrate 10 is 3.087 A ˚.…”

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confidence: 98%

“…Moreover, the latter is geometrically similar to an analogous nitrate … guanidinium interaction found in the crystal of tetrakis(guanidinium) tris(3-sulfonatophenyl)phosphine nitrate. 10 The former is of interest as a model of an anion … p system (see ref . 11).…”

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confidence: 99%

NO3–⋯NO3– and NO3–⋯π interactions in the crystal of urea nitrate

2007

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Formation and Solid State Structures of Highly Crystalline Guanidinium Salts of Sulfonated Tertiary Phosphanes

Cited by 15 publications

References 0 publications

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

[Tl^III(dota)]⁻: An Extraordinarily Robust Macrocyclic Complex

NO3–⋯NO3– and NO3–⋯π interactions in the crystal of urea nitrate

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Formation and Solid State Structures of Highly Crystalline Guanidinium Salts of Sulfonated Tertiary Phosphanes

Cited by 15 publications

References 0 publications

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative: Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

[TlIII(dota)]−: An Extraordinarily Robust Macrocyclic Complex

NO3–⋯NO3– and NO3–⋯π interactions in the crystal of urea nitrate

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[Tl^III(dota)]⁻: An Extraordinarily Robust Macrocyclic Complex