NMR titrations

The recognition of barium containing crown ether bridged chiral Schiff base zinc complex [44] with the rigid bidendate guest 1,4-diazobicyclo-[2,2,2]octane (DABCO) was studied by aH NMR titration.107... 

Noteworthy NMR studies involving nuclei other than phosphorus have been carried out for some P-chloro-NHPs where the possible occurrence of spontaneous P-Cl bond dissociation was probed by II NMR titrations and 35C1 NMR [20], and for P-cyclopentadienyl derivatives where measurement of solid-state 13C CP-MAS NMR spectra allowed one to substantiate the preservation of the circumambulatory ring migration of cyclopentadienyl groups in the solid state [47], Several neutral and cationic derivatives have also been studied by 15N NMR [20, 53],... 

Complexation of dendritic ligands 1 and 2 with lanthanide ions (Nd3+, Eu3+, Gd3+, Tb3+, Dy3+) [17f] leads to results qualitatively similar to those obtained upon Zn2+ complexation (see above) an increase in the monomer naphthalene emission band at 337 nm and a complete disappearance of the exciplex band at 480 nm. However, the complex stoichiometry is different. Emission data were best fitted considering the formation of 1 3 and 1 2 (metal/ligand) complexes (log f 1 2 = 14.1 and log [ivi = 20.0) in the case of 1 and a 1 3 (metal/ligand) complex (log / 1 3 = 20.3) for compound 2. Therefore, at low metal ion concentration, only the [M(2)3]3+ species is present, as also demonstrated by NMR titration. It is likely that in this complex... 

This Kd value was determined by NMR titration of FKBP with 1... 

Tab. 19.1 Chemical structures of needle molecules as found in the gyrase project. The KD values were determined by NMR titrations [17]...

Proton nmr titration experiments of [26] and [27] with KPF6 in acetonitrile revealed that in solution both compounds form 1 1 intramolecular sandwich complexes with the potassium cation. A number of alkyl-, vinyl- and azo-linked bis(benzo-15-crown-5) ligands are well known to exhibit this mode of K+ coordination. In the case of [26], a solid-state potassium complex was isolated whose elemental analysis and fast-atom bombardment mass spectrum ([26] K+ = 1083 complex ion) was in agreement with 1 1 complex stoichiometry (Fig. 20). 

The p-t-butylcalix[4]arenediquinone-bis(methylether) [56], which had previously been synthesized by Gutsche and co-workers, was used as a model compound in these studies. The receptors [54] and [55] have been shown by nmr titration techniques to form 1 1 solution state complexes with group 1 and 2 metal, ammonium and alkylammonium guest species. 

The addition of tetrabutylammonium chloride to H solutions of [68] and [69] in deuteriated acetonitrile resulted in remarkable nmr shifts of the respective proton signals of both receptors. Of particular note were the substantial downfield shifts of the amide protons (AS = 1.28 ppm for [68] and 1.52 ppm for [69]) on addition of one equivalent of chloride. These results suggest that a significant —CO—NH-Cr hydrogen-bonding interaction contributes to the overall anion complexation process. Subsequent nmr titration curves suggesting 1 1 stoichiometry with anion complexes of [68] and [69] were found in all cases. Negligible shifts were observed under identi-... 

Table 18 Stability constant data determined by nmr titration techniques. 

Recently a porphyrin unit has been incorporated into an anion receptor (Fig. 46) (Beer et al., 1995g). H nmr titration experiments with this compound demonstrated the formation of 1 1 stoichiometric complexes with tetrabutylammonium halides, nitrate, hydrogensulfate and dihydrogenphosphate. 

---