P NMR study of the stoichiometry, stability and thermodynamics of complex formation between palladium(II) acetate and bis(diphenylphosphino)ferrocene

The complexation reaction between palladium (II) acetate, and 1,1′-bis(diphenylphosphino)ferrocene, DPPF, was investigated in two different deuterated solvents CDCl₃ and DMSO at various temperatures using ³¹P NMR spectroscopy. The exchange between free and complexed DPPF is slow on the NMR time scale and consequently, two ³¹P NMR signals were observed. At metal ion-to-ligand mole ratio larger than 1, only one ³¹P NMR signal was observed, indicating the formation of a 1:1 Pd²⁺–DPPF complex in solution. The formation constant of the resulting 1:1 complexes was determined from the integration of two ³¹P signals. The values of the thermodynamic parameters (ΔH, ΔS and ΔG₂₉₈) for complexation were determined from the temperature dependence of stability constants. It was found that, in both solvents, the resulting complex is mainly entirely enthalpy stabilized and the ΔH compensates the TΔS contribution.     

The crystal and molecular structure of potassium aquapentachloroiridate(III) and the H, C, N NMR coordination shifts in iridium(III) chloride complexes with 2,2′-bipyridine or 1,10-phenanthroline

The crystal and molecular structure of potassium aquapentachloroiridate(III) (K₂[Ir(H₂O)Cl₅]) was reported. The [Ir(H₂O)Cl₅]²⁻ anions are nearly octahedral, the axial Ir–Cl bond (2.322(2) Å) being shorter than the equatorial ones (2.346(2)–2.360(2) Å); the Ir–O bond length is 2.090(4) Å. Ir(III) chloride complexes with 2,2′-bipyridine (LL = bpy) or 1,10-phenanthroline (LL = phen), of the general formulae K[Ir(LL)Cl₄] and cis-[Ir(LL)₂Cl₂]Cl, were studied by far-IR and ¹H–¹³C, ¹H–¹⁵N HMBC/HMQC/HSQC–NMR. High-frequency ¹H NMR coordination shifts (Δ^1H_coord = δ^1H_complex − δ^1H_ligand; max. ca. +1 ppm) were noted for [Ir(LL)Cl₄]⁻ anions, while for cis-[Ir(LL)₂Cl₂]⁺ cations they had variable sign and magnitude (max. ca. ±1 ppm); they were dependent on the proton position, being mostly expressed for the nitrogen-adjacent hydrogens (H(6) for bpy, H(2) for phen). ¹³C NMR signals were high-frequency shifted (by max. ca. 8 ppm), whereas all ¹⁵N nuclei were shifted to the lower frequency (by ca. 105–120 ppm). The experimental ¹H, ¹³C, ¹⁵N NMR chemical shifts were reproduced by semi-empirical quantum-chemical calculations (B3LYP/LanL2DZ+6-31G^**//B3LYP/LanL2DZ+6-31G*).     

Synthesis and Characterization of O,S-Dimethylphosphoramidothioate and N-Acetyl O,S-Dimethylphosphoramidothioate

O,S-Dimethylphosphoramidothioate (methamidophos) and N-acetyl O,S-dimethylphos- phoramidothioate (acephate) were synthesized by new methods to investigate the structure–activity study of acetyl cholinesterase (AChE) inhibition through the parameters of logP, δ ³¹P, and IC₅₀. After their characterization by NMR (³¹P, ³¹P{ ¹H}, ¹³C, and ¹H), IR, and mass spectroscopy, logP and δ ³¹P (³¹P chemical shift in NMR) were used to evaluate lipophilicity and electronical properties. The logP values for methamidophos and acephate were experimentally determined by the GC-shake-flask method, and the ability of the compounds to inhibit human AChE was evaluated by a modified Ellman's assay.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Direct hydrogen-1, carbon-13, and nitrogen-15 NMR study of magnesium(II)-isothiocyanate complexing

A hydrogen-1, carbon-13, and nitrogen-15 NMR study of magnesium(II)-isothiocyanate complexation in aqueous mixtures has been completed. At temperatures low enough to slow proton and ligand exchange, separate¹H,¹³C, and¹⁵N NMR signals are observed for coordinated and bulk water molecules and anions. The¹H NMR spectra reveal signals for the hexahydrate and the mono-through triisothiocyanato complexes, as well as two small signals attributed to [Mg(H₂O)₅(OH)]¹⁺ and [Mg(H₂O)₄(OH)(NCS)]. Accurate hydration numbers were obtained from signal area integrations at each NCS^– concentration. In the¹⁵N NMR spectra, signals also were observed for the mono-through triisothiocyanato complexes, and a small signal believed to be due to [Mg(H₂O)₄(OH)(NCS)]. Coordination number contributions for NCS^– were measured from these spectra and when combined with the hydration numbers they totalled essentially six at each anion concentration. Signals for [Mg(H₂O)₅(NCS)]¹⁺ through [Mg(H₂O)₃(NCS)₃]^1– also were observed in the¹³C NMR spectra and the area evaluations were comparable to the¹⁵N NMR results. An analysis of the magnitude and sign of the coordinated NCS^– chemical shifts identified the nitrogen atom as the anion binding site. All spectra indicated [Mg(H₂O)₅(NCS)]¹⁺ and [Mg(H₂O)₄(NCS)₂] were the dominat isothiocyanato complexes over the entire range of anion concentrations. The inability to detect evidence for complexes higher than the triisothiocyanato reflects the competitive binding ability of water molecules and perhaps the decreased electrostatic interaction between NCS^– and negatively charged higher complexes.     

Multinuclear NMR studies on substituted derivatives of Rh6(CO)16 in solution

Multinuclear NMR data (¹³C, ³¹P, ¹³C–{³¹P}, ¹³C–{¹⁰³Rh} and ³¹P–{¹⁰³Rh}) for a series of mono- and di-substituted derivatives of Rh₆(CO)₁₆ containing neutral two electron donor ligands [Rh₆(CO)₁₅L, (L=NCMe, py, cyclooctene, PPh₃, P(OPh)₃,1/2(μ₂,η¹:η¹-dppe)); Rh₆(CO)₁₄(LL), (LL=cis-CH₂=CMe-CMe=CH₂, dppm, dppe, (P(OPh)₃)₂)] are reported; these data show that the solid state structure is maintained in solution. Detailed assignments of the ¹³CO NMR spectra of Rh₆(CO)₁₅(PPh₃) and Rh₆(CO)₁₄(dppm) clusters have been made on the basis ¹³C–{¹⁰³Rh} double resonance measurements and the specific stereochemical features of the observed long range couplings in these clusters have been studied. The stereochemical dependence of ³J(P–C) for terminal carbonyl ligands is discussed and the values of ³J(P–C) are found to be mainly dependent on the bond angles in the P–Rh–Rh–C fragment; these data enable the fine structure of the complex multiplets in the ¹³C–{¹H} and ³¹P–{¹H} NMR spectra of Rh₆(CO)₁₄ (dppm) to be simulated. Variable temperature ¹³C–{¹H} NMR measurements on Rh₆(CO)₁₅(PPh₃) reveal the carbonyl ligands in this complex to be fluxional. The fluxional process involves exchange of all the CO ligands except the two terminal CO's associated with the rhodium trans to the substituted rhodium and can be explained by a simple oscillation of the PPh₃ on the substituted rhodium atom aided by concomitant exchange of the unique terminal CO on this rhodium with adjacent μ₃-CO's.     

Synthesis,Crystal Structure and Characterization of Hexakis[2‐methoxy‐4‐formylphenoxy]cyclotriphosphazene

The new cyclotriphosphazene derivative N₃P₃(OC₆H₃OCH₃COH)₆ ( 1 ) was synthesized from hexachlorocyclotriphosphazene, N₃P₃Cl₆, and 4‐hydroxy‐3‐methoxybenzaldehyde in acetonitrile in the presence of K₂CO₃. The structure of 1 was verified by means of elemental analysis, IR, ¹H NMR, ¹³C NMR, ³¹P NMR spectra, thermal analysis and X‐ray diffraction.     

Phase diagram and phase structure of the sodium di-n-pentyl phosphate-water system.1H pulsed-gradient NMR self-diffusion,31P NMR and x-ray diffraction studies

Sodium di-n-pentylphos phate (DPP) has been synthesized, and the phase diagram of the DPP-water system consisting of five regions (I, II, III, IV, and V) has been determined. The phase structure has been investigated by¹H pulsed-gradient NMR self-diffusion,³¹P NMR and x-ray low angle diffraction methods. The results are summarized as follows. In region I, there exist two critical micelle concentrations (CMC), indicating that this region is in a monomer-micelle equilibrium and that variation in the aggregated state occurs at the second CMC. Region II is a two phase area in which regions I and IV coexist. In region III, hydrated crystals and an aqueous solution of DPP coexist. Region IV is a homogenous, transparent and fluid phase and the results of³¹P NMR spectra and x-ray diffraction patterns reveal the formation of a highly organized structure, similar to a lamellar-like structure. Region V is a homogenous, transparent and fluid phase and the self-diffusion coefficient value and³¹P NMR spectra show that its phase structure is very similar to that for the concentrated sample in region I.     

Synthesis,Spectroscopy, X‐ray Crystallography,and DFT Computations of Nanosized Phosphazenes

Nanoparticles of nine phosphazenes with general formula 4‐CH₃C₆H₄S(O)₂N=PX₃ [X = Cl ( A ), NC₄H₈ ( 1 ), NC₆H₁₂ ( 2 ), NC₄H₈N–C(O)OC₂H₅ ( 3 ), NC₄H₈N–C(O)OC₆H₅ ( 4 ), NC₄H₈O ( 5 ), NHCH₂–C₄H₇O ( 6 ), N(CH₃)(C₆H₁₁) ( 7 ), NHCH₂–C₆H₅ ( 8 ), and 2‐NH‐NC₅H₄ ( 9 )] were synthesized using ultrasonic method and characterized by ¹H, ¹³C, ³¹P NMR, FT‐IR, fluorescence, as well as UV/Vis spectroscopy and additionally with XRD, FE‐SEM, N₂ sorption, and elemental analysis. The ³¹P NMR spectra of compounds 1 – 9 reveal the most up field shift δ(³¹P) for 9 at –11.45 ppm reflecting the most electron donation of 2‐aminopyridinyl rings through resonance to the phosphorus atom. The ¹H, ¹³C NMR spectra of 7 exhibit two sets of signals for the hydrogen and carbon atoms of its two isomers present in the solution state in 1:4 ratio. The FE‐SEM micrographs illustrate that the nanoparticles of compounds 1 – 9 have spherical morphology and a size of 27–42 nm. From the XRD patterns, the crystal sizes were estimated to about 24–86 nm. The highest bandgap was measured for 3 (3.81 eV) whereas the smallest was measured for 8 (3.50 eV). The structures of two polymorphs of compound 5 ( 5 , 5′ ) were determined by X‐ray crystallography at 120 K. Both of these polymorphs are triclinic with P1 space group but 5 has a doubled unit cell volume and two symmetrically independent molecules ( 5a and 5b ). In structures 5a and 5′ , the phosphorus and all endocyclic atoms of two morpholinyl rings display disorder, whereas the molecule 5b does not show disorder. The strong intermolecular O–H ··· O hydrogen bonds plus weak intermolecular C–H ··· O and C–H ··· N interactions create three‐dimensional polymers in the crystalline networks of 5 and 5′ . The DFT computations illustrate that molecule 5b is more stable than 5a by –1.1062 and –0.9779 kcal · mol^–1 at B3LYP and B3PW91 levels, respectively. The NBO calculations presented sp³d hybridization for phosphorus and sulfur atoms and sp², sp³ hybrids for the nitrogen and oxygen atoms.     

Titanium(IV) polynuclear hydroxo complexes stabilized in solution by [PW11O39]7? heteropolyanion

[PW₁₁O₃₉]^7– heteropolyanion (HPA) stabilizes Ti(IV) in aqueous solution at Ti:PW₁₁ ratios from 1 to 12 and pH 1–3. Ti(IV) is completely precipitated under these conditions in the absence of HPA. Differential dissolution phase analysis, optical, IR,³¹P and¹⁷O NMR spectra show that one Ti(IV) ion is incorporated into the Keggin lattice. The other ions, most probably, are located on the HPA surface in the form of oligomeric hydroxo fragments: [PW₁₁Ti^IVO₄₀·Ti_n–1 ^IVO_xH_y]^k–. Both types of Ti(IV) ions bind peroxo groups on interaction of the complex with H₂O₂.     

Structural features of potassium and cesium dodecahydro-closo-dodecaborates(2-) according to1H and11B NMR data

The structural and dynamic characteristics of the salts K₂B₁₂H₁₂ (I) and Cs₂B₁₂H₁₂ (II), containing an icosahedral closo-anion B₁₂H₁₂ ^2-, were investigated by the NMR method. Disagreement was found between the obtained NMR data and the published results from an x-ray crystallographic analysis with respect to the position of the H and B atoms in the crystal lattices of the compounds. The¹H and¹¹B NMR data give reason to suppose that compounds (I) and (II) can be assigned to the quasiperiodic crystal class with respect to the positions of the H and B atoms. From analysis of the line shapes in the¹H NMR spectra the interatomic separations r(B-H) in the B₁₂H₁₂ ^2– anion in the salts (I) and (II) were determined (1.21±0.01 Å). Activation dynamics characterized by activation barriers of 54.4 and 38.9 kJ/mole respectively were obtained for the B₁₂H₁₂ ^2– anions.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 2, pp. 79–83, March–April, 1993.     

Synthesis and characterization of a new cyclic phosph(V)azane ligand [(C6H5N)P(O)H]2 and its zinc(II) complex

The new cyclic phosph(V)azane ligand [(C₆H₅N)P(O)H]₂ (2) is obtained from the reaction between PCl₃ and PhNH₂ in toluene followed by controlled hydrolysis of the product in an H₂O–CHCl₃ solution. Compound 2 is the first example of P(V) dimer [(µ-NC₆H₅)P(H)=O]₂, a P₂N₂ ring with two P(O)H moieties. The reaction of 2 with ZnCl₂ in a molar ratio of 1?:?1 in tetrahydrofuran yields the cyclophosph(V)azane complex Cl₂Zn[(C₆H₅N)P(O)H]₂ (3) in which Zn–O bonds form directly between a cyclic phosph(V)azane ligand and Zn(II). The products have been characterized by infrared, multinuclear (¹H, ³¹P, ¹³C) NMR, mass spectrometry, and elemental analysis.     

Preparation,Characterization, and X-Ray Structure Analysis of 1,4-Diazabicyclo-2,2,2-octane (DABCO) and Ammonium Cation with Tetrathiomolybdate Anion

The reaction of H₂S gas with an aqueous solution of ammonium heptamolybdate in the presence of 1,4-diazabicyclo-2,2,2-octane (DABCO) led to the formation of a red colored complex. The complex was recrystallized in hot water and characterized by elemental analysis and UV-Visible, FT-IR, and ¹H NMR spectroscopy. The single sharp peak in the ¹H NMR spectrum has revealed that all the methylene protons are equivalent due to the hydrogen resonating between the two nitrogens in the DABCO cation. The complex crystallizes in a cubic system with space group P2₁3, a = 10.9482(9) Å, α = 90°, V = 1325.3(7) ų, R ₃ = 0.0154, wR ₂ = 0.038, Z = 4. The structure consists of the tetrahedral tetrathiomolybdate anions, which form an extended three-dimensional network in the solid state involving Mo-S...H-N hydrogen bonding interactions with DABCO and the ammonium cation.Original Russian Text Copyright © 2004 by S. Pokhrel, K. S. Nagaraja, B. Varghese__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 945–949, September–October, 2004.     

Molybdenum-95 nuclear magnetic resonance of a series of phosphine and phosphite substituted molybdenum carbonyls Mo(CO)6−n (L) n (n=1, 2, 3, 4, 5)

Molybdenum-95 NMR spectra of a series of phosphine and phosphite substituted molybdenum carbonyls Mo(CO)_6-n L _n [L=P(OCH₃)₃ n=1, 2, 3, 4, 5,L=P(OC₂H₅)₃ n=1, 2, 3,L=P(C₆H₅)₃ n=1] including isomers (cis,trans,fac,mer) are reported, A large range of chemical shifts is found for the title compounds. The coupling constants¹ J(⁹⁵Mo-³¹P) are derived either from⁹⁵Mo-NMR spectra or³¹P-NMR spectra. Syntheses of the measured compounds were performed by thermal or photochemical ligand substitution.

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Molybdän-95 NMR einer Reihe von Phosphin- und Phosphit-substituierten Molybdäncarbonylen Mo(CO)_6–n(L) _n (n=1, 2, 3, 4, 5)

Zusammenfassung Es werden die⁹⁵Mo-NMR-Spektren der im Titel genannten Verbindungen mitL=P(OCH₃)₃ n=1–5,L=P(OC₂H₅)₃ n=1–3 undL=P(C₆H₅)₃ n=1, einschließlich von Isomeren (cis, trans, fac, mer) angegeben. Für die chemischen Verschiebungen wurde ein sehr weiter Bereich beobachtet. Die Kopplungskonstanten¹ J(⁹⁵Mo-³¹P) wurden entweder von den⁹⁵Mo- oder³¹P-NMR-Spektren ermittelt. Die Synthese der Verbindungen erfolgte mittels thermischem oder photochemischem Ligandenaustausch.

     

Five-coordinate pentafluorobenzothiolate osmium(IV) complexes [Os(SC6F5)4(P(C6H4X-4)3)] (X = OCH3, CH3, F, Cl or CF3): Solid and solution structural characterization

The reactions of OsO₄ with excess of HSC₆F₅ and P(C₆H₄X-4)₃ in ethanol afford the five-coordinate compounds [Os(SC₆F₅)₄(P(C₆H₄X-4)₃)] where X = OCH₃ 1a and 1b, CH₃ 2a and 2b, F 3a and 3b, Cl 4a and 4b or CF₃ 5a and 5b. Single crystal X-ray diffraction studies of 1 to 5 exhibit a common pattern with an osmium center in a trigonal-bipyramidal coordination arrangement. The axial positions are occupied by mutually trans thiolate and phosphane ligands, while the remaining three equatorial positions are occupied by three thiolate ligands. The three pentafluorophenyl rings of the equatorial ligands are directed upwards, away from the axial phosphane ligand in the arrangement “3-up” (isomers a). On the other hand, ³¹P{¹H} and ¹⁹F NMR studies at room temperature reveal the presence of two isomers in solution: The “3-up” isomer (a) with the three C₆F₅-rings of the equatorial ligands directed towards the axial thiolate ligand, and the “2-up, 1-down” isomer (b) with two C₆F₅-rings of the equatorial ligands directed towards the axial thiolate and the C₆F₅-ring of the third equatorial ligand directed towards the axial phosphane. Bidimensional ¹⁹F–¹⁹F NMR studies encompass the two sub-spectra for the isomers a (“3-up”) and b (“2-up, 1-down”). Variable temperature ¹⁹F NMR experiments showed that these isomers are fluxional. Thus, the ¹⁹F NMR sub-spectra for the “2-up, 1-down” isomers (b) at room temperature indicate that the two S-C₆F₅ ligands in the 2-up equatorial positions have restricted rotation about their C–S bonds, but this rotation becomes free as the temperature increases. Room temperature ¹⁹F NMR spectra of 3 and 5 also indicate restricted rotation around the Os–P bonds in the “2-up, 1-down” isomers (b). In addition, as the temperature increases, the ¹⁹F NMR spectra tend to be consistent with an increased rate of the isomeric exchange. Variable temperature ³¹P{¹H} NMR studies also confirm that, as the temperature is increased, the a and b isomeric exchange becomes fast on the NMR time scale.     

Alkylhydrazides and their protonated forms: Physical methods andab initio calculations

The basicity of hydrazides of the highest aliphatic carboxylic acids RC(O)NHNH₂ (R = C_nH_2n+1,n = 5-12) has been studied by potentiometric titration, and IR and¹H NMR spectroscopy.Ab initio Hartree-Fork calculations using the 6–31G^* basis set with full optimization of geometry were carried out on the simplest acy1hydrazines and their possible protonated forms. Based on these calculations, and the 1R and¹H NMR spectra, the tautomerism of alkylhydrazides and the structures of their protonated forms are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2645–2649, November, 1996.     

Synthesis, characterization and crystal structure determination of platinum(IV) complexes containing, bipyridine derivatives and chloride, [Pt(5,5′-dmbipy)Cl4] and [Pt(6-mbipy)Cl4]

The complex [Pt(5,5′-dmbipy)Cl₄] (1) (5,5′-dmbipy is 5,5′-dimethyl-2,2′-bipyridine) was prepared from the reaction of H₂PtCl₆·6H₂O with 5,5′-dimethyl-2,2′-bipyridine in methanol. The same method was employed to make [Pt(6-mbipy)Cl₄] (2) (6-mbipy is 6-methyl-2,2′-bipyridine). Both complexes were characterized by elemental analysis, IR, UV–Vis, ¹H NMR, ¹³C NMR and ¹⁹⁵Pt NMR spectroscopy. Their solid state structures were determined by the X-ray diffraction method.     

Dihydrogen Splitting by Intramolecular Borane-Phosphane Frustrated Lewis Pairs: A Comprehensive Characterization Strategy Using Solid State NMR and DFT Calculations

Four hydrogenated intramolecular phosphane-borane frustrated Lewis pair (B/P FLP) compounds bearing unsaturated cyclic or aromatic carbon backbones have been synthesized and structurally characterized using ¹¹B, ³¹P, ¹H and ²H solid-state NMR spectroscopy. A comparison of the spectra with those of the corresponding free B/P FLPs shows that both ¹¹B isotropic chemical shifts as well as nuclear electric quadrupolar coupling constants decrease significantly upon FLP hydrogenation, revealing the breakage of the partial B−P bond present in the starting materials. Likewise, the ³¹P isotropic chemical shift, the chemical shift anisotropy, and the asymmetry parameter decrease significantly upon FLP hydrogenation, reflecting the formation of a more symmetric, C_3v-like local environment. ¹¹B{³¹P} rotational echo double resonance (REDOR) experiments can be used to measure the B−P internuclear distance (about 3.2 Å) of these compounds. Observation of the hydrogen atoms bound to the Lewis centers is best accomplished via ³¹P{¹H} and ¹¹B{¹H} cross-polarization-heteronuclear correlation experiments or by direct observation of the ²H MAS NMR signals on especially prepared FLP-D₂ adducts. For accurately measuring the phosphorus-deuterium distance via ³¹P{²H} rotational echo adiabatic passage double resonance (REAPDOR), it is essential to take the secondary dipolar coupling of ³¹P with the boron-bonded ²H nuclei explicitly into consideration, by simulating a ²H_P-³¹P-²H_B three-spin system based on structural input. All of the experimental NMR interaction parameters are found in excellent agreement with values calculated by DFT methods, using the geometries obtained either by energy optimization or from single-crystal structures.     

Synthesis and structural features of 1,3,2,5-dioxaboraphosphorinane complexes with Pt(II) and Pd(II) salts

Complexes of composition L₂MCl₂ [M=Pt, R=H (I), Me (II), Ph (III)], and LMC1₂ [M=Pd, R=H (IV)] are prepared by reaction of 4,6-R₂-2,5-diphenyl-1,3,2,5-dioxaboraphosphorinanes (L) with MCl₂. Far-IR and³¹P NMR spectroscopy are used to demonstrate that I is cis whereas II and III are trans complexes in the solid. The conformational behavior of I is studied by³¹P and¹H NMR. The asymmetric form of I exhibits anomalous stability.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2309–2312, October, 1991.     

A high-resolution phosphorus-31 nuclear magnetic resonance (NMR) spectroscopic method for the non-phosphorus markers of chemical warfare agents

A high-resolution phosphorus-31 nuclear magnetic resonance (NMR) spectroscopic method has been developed for detection, identification and quantification of non-phosphorus markers of toxic nerve agents (soman and V-class), vesicants (HD, HN-2, HN-3), and incapacitating agent (Bz). These analytes were converted to phosphorus-containing derivatives via phosphitylation reaction of their hydroxyl and sulfhydryl functions (using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane). This was followed by ³¹P{¹H} and ³¹P NMR analysis of these derivatives. The chemical shifts (δ) and coupling constants (³ J _P–H) of derivatives were used for their specific detection and identification. The method allowed clear distinction between the alcohols and thiols. The lower limits of detection of these analytes were found to be between 12 and 28 μg obtained from 128 transients of ³¹P{¹H} quantitative NMR experiments. Utility of the method was ensured by the detection and identification of triethanolamine present (at an original concentration of 5 μg/mL) in an aqueous sample from 28th OPCW Official Proficiency Tests.