Linking 31P magnetic shielding tensors to crystal structures: experimental and theoretical studies on metal(II) aminotris(methylenephosphonates).

The (31)P chemical shift tensor of the phosphonate group [RC-PO(2)(OH)](-) is investigated with respect to its principal axis values and its orientation in a local coordinate system (LCS) defined from the P atom and the directly coordinated atoms. For this purpose, six crystalline metal aminotris(methylenephosphonates), MAMP·xH(2)O with M = Zn, Mg, Ca, Sr, Ba, and (2Na) and x = 3, 3, 4.5, 0, 0, and 1.5, respectively, were synthesized and identified by diffraction methods. The crystal structure of water-free BaAMP is described here for the first time. The principal components of the (31)P shift tensor were determined from powders by magic-angle-spinning NMR. Peak assignments and orientations of the chemical shift tensors were established by quantum-chemical calculations from first principles using the extended embedded ion method. Structure optimizations of the H-atom positions were necessary to obtain the chemical shift tensors reliably. We show that the (31)P tensor orientation can be predicted within certain error limits from a well-chosen LCS, which reflects the pseudosymmetry of the phosphonate environment.

Calcium-phosphonate interactions: solution behavior and Ca2+ binding by 2-hydroxyethylimino-bis(methylenephosphonate) studied by multinuclear NMR spectroscopy.

The tetra-acid 2-hydroxyethylimino-bis(methylenephosphonic acid) (HEIBPH, 1) and its ring condensation product, the triacid 2-hydroxy-2-oxo-4-phosphonemethyl-1,4,2-oxazaphosphorinane (2), were investigated for determination of protonation constants using (31)P, (1)H, and (13)C NMR spectroscopy in a wide pH range. As for other alpha-amino-phosphonic acids, the first protonation of 1 is straightforward and occurs at the nitrogen, while for 2 the first protonation occurs simultaneously at the exo phosphonate group, allowing estimation of the microscopic protonation constants. The complexation of Ca(2+) with 1 in a 1:1 molar ratio in aqueous solutions and in the presence of a 5-fold excess Na(+) is rationalized by the products LCaH(2), LCaH, LCaNaH, LCa, and LCa(2) (L = 1). Only the phosphonate groups are involved in Ca(2+) binding at pH > 3, while the phosphonate, hydroxyl, and amine functionalities coordinate to Ca(2+) at pH > 6-7, as soon as the proton at N is lost. Probable conformation states of ions of 1 and 2 are estimated by means of the dependence of vicinal coupling constants (3)J(HH) and (3)J(PC) from dihedral angles.

The proton nuclear magnetic shielding tensors in biphenyl: experiment and theory.

Line-narrowing multiple pulse techniques are applied to a spherical sample crystal of biphenyl. The 10 different proton shielding tensors in this compound are determined. The accuracy level for the tensor components is 0.3 ppm. The assignment of the measured tensors to the corresponding proton sites is given careful attention. Intermolecular shielding contributions are calculated by the induced magnetic point dipole model with empirical atom and bond susceptibilities (distant neighbours) and by a new quantum chemical method (near neighbours). Subtracting the intermolecular contributions from the (correctly assigned) measured shielding tensors leads to isolated-molecule shielding tensors for which there are symmetry relations. Compliance to these relations is the criterion for the correct assignment. The success of this program indicates that intermolecular proton shielding contributions can be calculated to better than 0.5 ppm. The isolated-molecule shielding tensors obtained from experiment and calculated intermolecular contributions are compared with isolated-molecule quantum chemical results. Expressed in the icosahedral tensor representation, the rms differences of the respective tensor components are below 0.5 ppm for all proton sites in biphenyl. In the isolated molecule, the least shielded direction of all protons is the perpendicular to the molecular plane. For the para proton, the intermediate principal direction is along the C-H bond. It is argued that these relations also hold for the protons in the isolated benzene molecule.

X-ray, 31P CP/MAS, and single-crystal NMR studies, and 31P DFT GIAO calculations of inclusion complexes of bis[6-O,6-O'-(1,2:3,4- diisopropylidene-alpha-D-galactopyranosyl)thiophosphoryl] disulfide: the importance of C-H...S=P contacts in the solid state.

Bis[6-O,6-O'-(1,2:3,4-diisopropylidene-alpha-D-galactopyranosyl) thiophosphoryl] disulfide shows a strong tendency to form inclusion compounds. The crystal and molecular structure of eight different solvates was established by X-ray analysis. The results indicate three different types of disulfide arrangements in the crystal lattice. By means of 31P CP/MAS NMR experiments the principal values delta 11, delta 22, and delta 33 of the 31P chemical shift tensor were obtained for each form. The orientation of its principal axes with respect to a molecular frame was investigated by means of 31P CP and single-crystal NMR for the complex with propan-2-ol. The principal axis 1 of both chemically equivalent phosphorus atoms is nearly parallel to the P-S bond and the principal axis 3 is very close to the P=S bond. DFT GIAO calculations of the model compound (EtO)2(S)P1SSP2(S)-(OEt)2 allowed assignment of the experimental chemical shift curves to the magnetically nonequivalent atoms P1 and P2. The maximum difference between calculated angles [symbol: see text] i-P-X)calcd and experimental angles [symbol: see text] i-P-X)exptl is 8.3 degrees and the rms distance 3.8 degrees (i = principal axes 1, 2, 3; X = S, -S-, -O1-, -O2-). The influence of C-H...S weak hydrogen bonding on phosphorus shielding was tested theoretically (31P DFT GIAO) employing the dimethoxythiophosphoryl disulfide.CH4 complex as a model compound. The sensitivity of 31P delta ii parameters to intermolecular forces is demonstrated.