4441-17-2

A new six-coordinate organotin(IV)-phosphoric triamide complex of OP[NC5H10]3?=?OP was synthesized ([Cl2Sn(CH3)2(OP)2], 1) and characterized by X-ray crystallography and spectroscopic methods (FT-IR, UV–Vis, and 1H/13C/31P-NMR). The crystal structures of 1 and the analogous previously reported five-coordinate complex [Cl2Sn(CH3)2(OP)] (IZOVIE) were compared on a structural level and by computational means using Hirshfeld surface analysis, density functional theory calculations and the atom in molecule method. The investigation of intermolecular interactions in the crystal structures of the two complexes by the Hirshfeld surface method indicates that in the absence of normal hydrogen bonds, the chlorine-based interactions H?Cl/Cl?H (for 1 and IZOVIE) and Cl?Sn/Sn?Cl (for IZOVIE) play a determinant role in the molecular assemblies. However, the prominent contacts are of H?H type. From calculated electronic parameters such as bond order, Mulliken charge and electron delocalization energy, it was found that the Sn-OP contact has a lower strength in IZOVIE than in 1, suggesting more ionic character of the metal-oxygen contact in five-coordinate complex IZOVIE. Furthermore, we discuss the similarities and differences of the two complexes 1 and IZOVIE derived from the same ligand OP by density functional theory calculations to present an insight into the organotin(IV)-phosphoric triamide coordination chemistry affected by different geometries and coordination numbers.

We report on a novel phosphoramide complex with formula Cu(NO3)2([C5H10N]3PO)2. This complex is the first example of a copper monomeric phosphoric triamide having an octahedral Cu[O]6coordination environment. Cu(NO3)2([C5H10N]3PO)2crystallizes in the monoclinic space group P21/n with the Cu atom located at an inversion center, as determined by single-crystal X-ray diffraction. Magnetic measurements along the principal crystallographic directions of the single crystal indicate that the complex is a paramagnet with very low magnetic anisotropy. Electron paramagnetic resonance spectra reveal the presence of two Cu2+sites and make it possible to extract the hyperfine coupling.

Hydroxide-stable organic cations are crucial components for ion-transport processes in electrochemical energy systems, and the tetrakis(dialkylamino)phosphonium cation is a promising candidate for this application. These phosphoniums are known to be highly resistant to alkaline media; however, very few investigations have systematically evaluated how these cations decompose in the presence of hydroxide or alkoxide anions. The excellent stability of several tetraaminophosphoniums in 2 M KOH/CH3OH at 80 °C led us to design experiments for the rapid assessment of phosphonium degradation in homogeneous solution and under phase-transfer conditions. The analysis illustrated how substituents around the cation core affect both degradation pathways and rates. β-H elimination and direct attack at the phosphorus atom are the most common degradation pathways observed in an alcoholic solvent, while α-H abstraction and direct attack are observed under phase-transfer conditions (PhCl and 50 wt % NaOH/H2O). The collected data provided a relative stability comparison for this family of cations to enable future design improvements and illustrated the utility of using multiple tests for degradation studies.

The present invention relates to mixtures comprising from 70 to 99.5% by weight of a compound of the formula (R)4P+X? (1) and from 30 to 0.5% by weight of a compound of the formula (R)3P=O (2), where R is in each case a radical and X? is an inorganic or organic anion or the equivalent of a multiply charged inorganic or organic anion, also to a process for preparing the mixtures by reacting a phosphorus pentahalide with pyrrolidine or piperidine in the molar ratio 1:6 to 1:50 in the presence of an inert solvent initially at ?20 to 80° C., subsequently continuing the reaction at 90 to 180° C., treating the resulting reaction product at 0 to 80° C. with aqueous alkali at a pH of 7 to 15, and separating aqueous and organic phase from one another, and to the use of the mixtures as catalyst and cocatalyst for phase-transfer reactions, nucleophilic substitution reactions or halogen-fluorine exchange reactions.

An organic carbonate such as dimethyl carbonate is prepared by reacting an alcohol such as methanol with carbon monoxide oxygen in the presence of a catalyst system containing Cu(OMe)Cl as a catalyst and a phosphoramide as an additive for the catalyst system.