Reaction of N-Phosphoryl(thio)amides with Stannic Chloride

N-Dialkoxyphosphinoylamides react with SnCl4 without rupture of the NH bonds to form stable 1:1 complexes. Replacement of one or both oxygen atoms in the P=O and C=O groups of these compounds by a sulfur atom changes the composition of the complexes and may result in an ionic mechanism of complexation. Nonacylated amidophosphate and thioamidophosphate form 2:1 and 1:1 complexes, respectively

Thermodynamics and Kinetics of Adduct Formation in Solutions of Bis(N-diisopropoxyphosphinoylthiobenzamido)-copper(II). An ESR Study and Description in Terms of the Donor-Acceptor Model

The equilibrium constants Kad, enthalpies, and entropies of adduct formation, rate constants for adduct formation (kf) and dissociation (kd), and enthalpies and entropies of activation have been calculated for solutions of bis(N-diisopropoxyphosphinoylthiobenzamido)copper(II) (CuL2) in toluene with addition of donor solvents Y (methanol, N,N-dimethylformamide, dimethyl sulfoxide, pyridine, piperidine, diethylamine) over a wide temperature range. The quantities logKad, logkf, and logkd have been found to linearly vary with the donor numbers of the solvents Y; on this basis, an associative character of activation in the formation and dissociation of adducts with copper(II) bischelates has been established for the first time. The constants Kad for CuL2Y are higher than those for other analogous adducts presumably due to the larger fraction of the isomer CuL2Yeq with equatorial coordination of the solvent

1,2-Benzo-15-crown-5 containing an N-thiophosphorylthiobenzamide fragment

A crown-containing N-thiophosphorylthioamide has been synthesised by a reaction between diisopropyl thiophosphate chloride and (4-amidothiocarbonyl-1,2-benzo)-15-crown-5, and its chelate complex with nickel(II) has been obtained

Synthesis and crystal structure of complexes of bipodal thiophosphorylated thioureas with divalent transition metals

According to X-ray crystallography, the title compounds exist as metallomacrocycles in the crystal. © 2004 Elsevier Ltd. All rights reserved

Self-assembly of the complexes of bipodal thiophosphorylated thioureas

N-Thiophosphorylated thioureas, of general formula [(i-PrO)2 P(S)NHC(S)]2Z (Z = α,ω-diamino(oxy)alkyl or 1,10-diaza-18-crown-6), in the form of potassium salts, react with a number of soft ions (Cd2+, Zn2+, Co2+, Ni2+, Pd2+) to form novel dimeric complexes. The cadmium (Z = HN(CH2)2NH), palladium (Z = HN(CH2)2O(CH2)2NH), and cobalt (Z = 1,10-diaza-18-crown-6) complexes were analyzed by x-ray crystallography. In the former complex, crown cavities remain free. This fact will allow us to obtain "guest-host" complexes with alkali metal cations

Synthesis and complexing properties of N-(thio)phosphorylated bis(thio)ureas

New phosphorus-containing podands, N-(thio)phosphorylated bis(thio)ureas, were prepared by reactions of α,ω-diamines with (thio)phosphoryl iso(thio)cyanates. Chelates of these compounds with some metal ions were isolated

Coordination diversity of N-phosphoryl-N′-phenylthiourea (LH) towards CoII, NiII and PdII cations: Crystal structure of ML2-N,S and ML2-O,S chelates

Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O) nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal field and the NH-O{double bond, long}P hydrogen bonds. © 2006 Elsevier B.V. All rights reserved

Reaction of N-Phosphoryl(thio)amides with Stannic Chloride

N-Dialkoxyphosphinoylamides react with SnCl4 without rupture of the NH bonds to form stable 1:1 complexes. Replacement of one or both oxygen atoms in the P=O and C=O groups of these compounds by a sulfur atom changes the composition of the complexes and may result in an ionic mechanism of complexation. Nonacylated amidophosphate and thioamidophosphate form 2:1 and 1:1 complexes, respectively

Reaction of o,o-diisopropyl dithiophosphate with nitriles of carboxylic acids

The interaction of O,O-diisopropyl dithiophosphate with benzonitrile, phenylacetonitrile, adipodinitrile, and ethyl cyanoacetate proceeds with the formation of unstable imidoyldithiophosphates, which are capable of being rearranged to form the corresponding phosphorylated thioamides. The further course of the reaction is associated with the splitting of the P-N-C or P-S-C bonds in the N-(O,O-diisopropylthiophosphonyl)thioamides and probably of the imidoyldithiophosphates under the action of a second molecule of the dithio acid. © 1979 Plenum Publishing Corporation