Thermochemistry of Vaporization and Solvation of Some Three- and Tetracoordinated Organophosphorus Compounds

Abstract

The vaporization and solvation enthalpies about 100 P(III)- and P(IV)-compounds of different acyclic and cyclic space structure have been determined and analysed.     

Hypercoordination in Organotin Chemistry – A Novel O,C,O-Coordinating Ligand

Recent results are reported on the application of the novel O,C,O-coordinating pincer ligand {2,6-[P(O)(OEt)₂]₂-4-tert-Bu-C₆H₂} (A) for the synthesis of hypercoordinate organotin(IV) compounds ASnR₃ (R = Ph, Cl), heteroleptic stannylenes ASnR (R = Cl, CH₂SiMe3) and intramolecularly coordinated 1,2,5-oxaphosphastannolanes.     

The Reactivity of Associates of Aminomethylated Calix [4] Resorcinolarenes towards P-Nitrophenyl Esters of Phosphorus Acids

Abstract

The kinetics of reactions of aminoinethylated calixarenes (AMC) of different structure (substituents at nitrogen atom as well as on the “lower” rim of cavity are varied) with esters of phosphorus acids has been studied under pseudofirst order conditions in water-DMF and water-alcohol (i-PrOH) solutions by spectrophotometry. The dependences of the observed rate constants of the reactions on the concentrations of AMC reach a plateaus at the investigated values of pH 8 - 1 1. This indicates binding of the substrates by the aggregates of AMC and allows to calculate the parameters of the reactions: CCA, k_a, K_b. It was shown by NMR ³¹P method, that AMC are the catalysts of hydrolysis of esters of phosphorus acids in water-DMF solutions. The higher reactivity of AMC as compared with the one of calix[4]resorcinolarenes and o-aminomethylphenols was found. It was revealed AMC preceeds in both media, however the reactivity of the aggregates is considerably less in the water - alcohol solutions than those in the water - DMF solutions.     

Study of “Racemic Compound-Like” Behavior of Diastereomeric Mixture of Pinanyl Sulfoxides by X-Ray Diffraction,IR Spectroscopy,and DFT Calculations

Abstract

The oxidation of a β-hydroxysulfide in the pinane series by use of m-chloroperbenzoic acid resulted in the formation of the corresponding β-hydroxysulfoxide as a mixture of two diastereomers in 4:5 ratio. According to single-crystal X-ray diffraction (XRD) results, it is established that the diastereomeric mixture of sulfoxides crystallizes in the “racemic compound-like” manner under formation of asymmetric dimers through S=O··H–O interactions. This asymmetric dimer formed from diastereomeric molecules is a structural unit in both crystal modifications, the triclinic and the monoclinic one. The behavior of the diastereomeric mixture of pinane derived sulfoxides in crystals, melts and in tetrachloromethane solutions was studied by IR spectroscopy. The density functional theory (DFT) method with 6-31G (d, p) basis set was used to calculate the optimized geometrical parameters and vibrational frequencies of different associates in solutions. The calculated vibrational frequencies are compared with experimental IR spectra.     

The Unexpected Formation of a 2,2′-Di( N -ethyl-acetamino)substituted Diphenyl Disulfane on Oxidation of 3-Ethyl-2-methylbenzothiazolium Tetrafluoroborate

Attempts at the oxidation of 3-ethyl-2-methylbenzothiazolium salt 2 with a variety of oxidizing reagents did not lead to the desired isochiral S -oxide 3 or achiral S , S -dioxide 4 , in some cases, however, unexpectedly to the ring-opened dimeric 2,2'-di( N -ethyl-acetamino)substituted diphenyl disulfane 5 , the molecular structure of which was confirmed by x-ray analysis. The synthesis of 2-methylbenzothiazole- S , S -dioxide 14 , reported by Zincke et al. in 1915, turned out to be not reproducible. \centerline{\epsfbox{:art:fig-01.jpg}}     

Unexpected but Easy Synthesis of a Dihydrophosphadiazaazulene

Abstract

The title compound is the main product of the 2:1 reaction of DMAD with diazaphosphinines. The supposed mechanisms with intermediates and related products will be presented.     

Phosphorinane and Enol Rings in One Molecule. Evidence for Reciprocal Stabilization of Half-Chair Conformations

Abstract.

The X-ray crystal structure of 2-(2′,4′-dioxo-3′-pentyl)-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane (2) reveals significant half-chair distortion of the axially oriented cisenol ring. The molecule also undergoes in-plane deformations. R(O...O) = 2.410 Å in the enol moiety indicates a very strong hydrogen bonding. The enol content, δ_OH and thermodynamic parameters for the axial-equatorial conformational and keto-enol equilibriums were obtained from ¹H, ³¹P NMR and IR measurements in comparison with the planar 4,6-dimethyl isomer (1) containing equatorially oriented enol ring. The X-ray single crystal structure of 5,5-dimethyl-2-(methoxycarbonyl-3′-oxo-2′-butyl)-2-oxo-1,3,2-dioxaphosphorinane (3) reveals the unusual half-chair conformation of the dioxaphosphorinane cycle disposed a trans-enol ring substituent. ¹H, ³¹P NMR and IR solution data support the same structure displays a strong conformational preference while the minor forms are chair conformers with an axial or equatorial cis-enol ring.     

Metal-Rich Phosphanediyl-and Arsanediyl-Clusters

Abstract

The reactions of primary silylphosphanes and -arsanes 1 with BuLi yield the three-dimensional M₂ER-aggregates 2 (E = P, As). We observed that the double lithiation of 1 in the presence of Li₂O results in the formation of the aggregates 3 and 4.     

Features of Phosphabutadienes Structure: Nmr Spectroscopy and X-Ray Investigation

Abstract

Conjugation effects in various phosphabutadienes are considered.