Organophosphorus Ligands Research Articles

Catalytic synthesis of propylene carbonate from propylene oxide and carbon dioxide in the presence of rhodium complexes modified with organophosphorus ligands and chitosan

The reaction between CO2 and propylene oxide to produce propylene carbonate in the presence of rhodium complexes modified with organophosphorus ligands and chitosan has been studied. Highly effective catalysts mediating the reaction with almost a 100% yield and 100% selectivity have been prepared using rhodium compounds modified with triphenylphosphine and chitosan.

Pd0‐Catalyzed Hydrogenolysis of a Bicyclic Allylic Diacetate

AbstractThe Pd0‐catalyzed hydrogenolysis of 2,3‐bis(acetoxymethyl)bicyclo[2.2.1]hepta‐2,5‐diene (1) is described. The influence of various hydride sources on the reaction, as well as different experimental conditions and organophosphorus ligands have been rigorously investigated.

Synergistic extraction of uranium(VI) and thorium(IV) with mixtures of Cyanex272 and other organophosphorus ligands

The extraction of thorium(IV) and uranium(VI) from nitric acid solutions has been studied using mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex272 or HA), and synergistic extractants (S) such as tri-butylphosphate (TBP), tri-octylphosphine oxide (TOPO) or bis(2,4,4-trimethylpentyl)thiophosphinic acid (Cyanex301). The results showed that these metallic ions are extracted into kerosene as Th(OH)2(NO3)A·HA and UO2(NO3)A·HA with Cyanex272 alone. In the presence of neutral organophosphorus ligands TBP and TOPO, they are found to be extracted as Th(OH)2(NO3)A·HA·S and UO2(NO3)A·HA·S. On the other hand, Th(IV), U(VI) are extracted as Th(OH)2(NO3)A·HA·2S and UO2(NO3)A·HA·S in the presence of Cyanex301. The addition of neutral extractants such as TOPO and TBP to the extraction system enhanced the extraction efficiency of both elements while Cyanex301 as an acidic extractant has improved the selectivity between uranium and thorium. The effect of TOPO on the extraction was higher than other extractants. The equilibrium constants of above species have been estimated by non-linear regression method. The extraction amounts were determined and the results were compared with those of TBP. Also, it was found that the binding to the neutral ligands by the thorium–Cyanex272 complexes follows the neutral ligand basicity sequence.

Organophosphorus ligands with XPNSO skeleton (X = O, S) and their Pd(II) complexes. Crystal and molecular structure of [{XP(OEt)2}(O2SR)]NH (X = O, R = Me, Ph; X = S, R = C6H4Cl-4) and Pd[{SP(OEt)2}(O2SC6H4Cl-4)N

Several organophosphorus acids of type [{XP(OEt)2}(O2SR)]NH [X=O, R=Me (1), Ph (2), C6H4CH3-4 (3); X=S, R=C6H4Cl-4 (4)] were obtained by a method based on the reaction between (EtO)2P(X)NHLi and the corresponding organosulfonyl chloride. They were subsequently deprotonated with KOBut. Salt metathesis reactions between PdCl2 and the corresponding potassium salts K[{XP(OEt)2}(O2SR)N] [X=O, R=Me (5), Ph (6), C6H4CH3-4 (7); X=S, R=C6H4Cl-4 (8)] in a 1:2 molar ratio resulted in palladium(II) complexes of type Pd[{XP(OEt)2}(O2SR)N]2 [X=O, R=Me (9), Ph (10), C6H4CH3-4 (11); X=S, R=C6H4Cl-4 (12)]. In a similar way was obtained the palladium(II) complex Pd[(SPPh2)(O2SPh)N]2 (13), using the appropriate reagents. All compounds were characterized by multinuclear NMR (1H, 13C, 31P) and infrared spectroscopy. The potassium salts and the palladium complexes were investigated also by mass spectrometry. Single-crystal X-ray diffraction studies revealed a layered supramolecular assembly in case of acid 1, a monomeric structure for compound 4, while in case of compound 2 dimeric associations are formed in the solid state by NH⋯OP hydrogen bonding. A trans-S,N-coordination pattern of the organophosphorus ligand was found in the palladium complex 12. Moreover, short Cl⋯H contacts result in a polymeric [Pd[{SP(OEt)2}(O2SC6H4Cl-4)N]2]n chain.

Extraction of Lanthanides(III), U(VI), and Th(IV) from Nitric Acid Solutions with 1,5-N,N'-Bis[(diphenylphosphoryl)acetylamino]pentanes

Novel polyfunctional neutral organophosphorus ligands, namely 1,5-N,N'-bis[(diphenylphosphoryl)acetyl(alkyl)amino]pentanes [Ph2P(O)CH2C(O)NR]2(CH2)5 (Ia, R = C6H13; Ib, R = CH3), were studied as extractants for Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U from nitric acid solutions. The effect of both HNO3 concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined by the slope analysis method. Compared with the related bisaminopentane [Ph2P(O)CH2C(O)NH]2(CH2)5 (Ic), the replacement of hydrogen atoms at the amide nitrogens by alkyl radicals (compounds Ia,b) leads to an increase of metal ions extraction. Bis-CMPO ligands Ia-c were found to possess higher extraction efficiency towards U(VI), Th(IV), and Ln(III) than their monophosphorylated analogue Ph2P(O)CH2C(O)N(C4H9)2.

Novel organotin(IV) complexes of organophosphorus ligands: Synthesis, spectroscopic, structural study and DFT calculations

Three new phosphoric triamides with general formula C6H5C(O)NHP(O)X2, where X = N-4-phenylpiperazinyl (1), N-4-ethoxycarbonyl piperazinyl (2), and N-4-ethoxycarbonyl piperidinyl (3) as well as seven novel organotin(IV) complexes with formula SnClR1R2R3L2 where R = alkyl/aryl/Cl and L = organophosphorus ligand, were synthesized and characterized by 1H, 13C, 31P NMR, IR spectroscopy and elemental analysis. The 31P{1H} NMR spectra of compounds 9 and 10 each reveal two close signals that are related to their cis and trans isomers. DFT calculations were performed at B3LYP and M06 methods with LanL2DZ basis set using Gaussian 09 software on the cis and trans configurations of compounds 9 and 10. The structure of compound 1 was determined by X-ray crystallography. In this structure, there are two symmetrically independent molecules (1 and 1A) produced due to the co-crystallization of water and CH3OH molecules. The PO and CO bonds in both molecules 1 and 1A indicate an anti conformation relative to each other. The strong intermolecular N–H⋯OP hydrogen bonds plus weak intermolecular C–H⋯O(1W), C–H⋯OC, C–H⋯OP and C–H⋯N hydrogen bonds create a three-dimensional polymeric chain in the crystalline network.

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf2N) has been studied. The effect of HNO3 concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf2N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.

Synthesis and evaluation of ligands with mixed amide and phosphonate, phosphinoxide, and phosphonothioate sites for An(iii)/Ln(iii) extraction

Various organophosphorus ligands with a combination of different donor sites were synthesized and evaluated by solvent extraction studies for the complexation of Am(III)/Eu(III). Among the ligands with a glycolamide backbone, those with mixed amide and PO donor sites and a central oxygen or nitrogen atom showed a reasonable extraction of Am(III) and Eu(III). Ligands with a central oxygen atom exhibited selectivity towards Eu(III), and those with a central nitrogen atom towards Am(III). Ligands with PS donor sites and a glycolamide backbone did not show any reasonable extraction. Amongst the ligands with a malonamide backbone, high extraction efficiency was observed for the ligand with electron-rich substituents on phosphorus, however, with almost no discrimination between Am(III) and Eu(III). The extraction efficiency of different ligands towards Eu(III) was confirmed by microcalorimetry.

Extraction of Lanthanide and Actinide Nitrate and Thiocyanate Salts by 2:6-Bis[(bis(2-n-Octyl)phosphino)methyl]pyridine N:P:P′-trioxide in Toluene

Organophosphorus reagents for solvent extraction have played a particularly important role in actinide science and technology. A wide variety of compounds of varying basicity, denticity, and geometric arrangement of donor groups have been reported. Of relevance to this report, some features of the extraction of actinides by 2,6-bis[(bis(2-ethylhexyl)phosphino)methyl]pyridine N,P,P′-trioxide, TEH(NOPOPO), have been previously reported. The presence of a chiral center at the ethylhexyl groups makes purification difficult, though its solubility is improved by the presence of four chiral centers. In contrast, the structurally-related extractant 2,6-bis[(bis(2-n-octyl)phosphino)methyl] pyridine N,P,P′-trioxide, TO(NOPOPO), can be purified by crystallization (at the price of lower solubility limits relative to TEH(NOPOPO). This work reports new results describing the extraction of Am(III), Th(IV), Pu(IV), Np(V), and U(VI) from acidic nitrate and thiocyanate media by the trifunctional organophosphorus ligand TO(NOPOPO)) in toluene. Trans-lanthanide trends for extraction are also explored. TO(NOPOPO) behaves as a classic solvating extractant reagent, wherein extraction preference increases as the effective charge of actinide metal cation increases. The corresponding lanthanide extraction patterns are either flat (nitrate) or tending to discriminate between light and heavy lanthanides (thiocyanate). The extractant stoichiometry of the phase transfer reaction of the actinides into TO(NOPOPO) in toluene varies between 1 and 2 for the suite of metal nitrates and thiocyanates investigated. The back extraction of trivalent ions and Np(V) can be accomplished with a shift to less acidic media, but stripping of hexavalent and tetravalent ions requires a complexant. Results indicate that TO(NOPOPO) in toluene is a strong extractant for actinide nitrates in all oxidation states and potentially a suitable platform to explore for trivalent actinide-lanthanide separations from thiocyanate media.

Hypervalent Organoselenium(II) Compounds with Organophosphorus Ligands. Crystal and Molecular Structure of [2‐(iPr2NCH2)C6H4]Se[S2PR'2] (R'; = Ph, OiPr)

Hypervalent Organoselenium(II) Compounds with Organophosphorus Ligands. Crystal and Molecular Structure of [2‐(iPr₂NCH₂)C₆H₄]Se[S₂P<i>R'</i>₂] (<i>R'</i>; = Ph, O<i>i</i>Pr)

Hypervalent Organoselenium(II) Compounds with Organophosphorus Ligands. Crystal and Molecular Structure of [2‐(iPr2NCH2)C6H4]Se[S2PR′2] (R′ = Ph, OiPr)

AbstractRedistribution reactions between diorganodiselenides of type [2‐(R2NCH2)C6H4]2Se2 [R = Et, iPr] and bis(diorganophosphinothioyl disulfanes of type [R′2P(S)S]2 (R = Ph, OiPr) resulted in the hypervalent [2‐(R2NCH2)C6H4]SeSP(S)R′2 [R = Et, R′ = Ph (1), OiPr (2); R = iPr, R′ = Ph (3), OiPr (4)] species. All new compounds were characterized by solution multinuclear NMR spectroscopy (1H, 13C, 31P, 77Se) and the solid compounds 1, 3, and 4 also by FT‐IR spectroscopy. The crystal and molecular structures of 3 and 4 were determined by single‐crystal X‐ray diffraction. In both compounds the N(1) atom is intramolecularly coordinated to the selenium atom, resulting in T‐shaped coordination arrangements of type (C,N)SeS. The dithio organophosphorus ligands act monodentate in both complexes, which can be described as essentially monomeric species. Weak intermolecular S···H contacts could be considered in the crystal of 3, thus resulting in polymeric zig‐zag chains of R and S isomers, respectively.

N-(1,5-dimethyl-3-oxo-2-phenyl-1,2-dihydropyrazol-4-yl)-P,P-diphenylamidophosphinate and its complexes with neodymium(III), erbium(III), thorium(IV), and uranyl nitrates: Synthesis and crystal and molecular structure

A new phosphoryl-containing ligand based on 4-aminoantipyrine-N-(1,5-dimethyl-3-oxo-2-phenyl-1,2-dihydropyrazol-4-yl)-P,P-diphenylamidophosphinate (L) was synthesized. In crystals, the L molecules were found to be combined in centrosymmetric dimers through N-H…O=C hydrogen bonds. The complexes of L with neodymium(III), erbium(III), thorium(IV), and uranyl nitrates were obtained, and their structures were determined. The bands of the C=O and P=O groups in the IR spectra of these complexes are shifted toward low frequencies (by 50–65 and 40–70 cm−1, respectively), which is indicative of a bidentate coordination of the organophosphorus ligand. According to the X-ray crystallography data, uranyl is bidentately coordinated by both the L molecule (through the C=O and P=O groups) and two nitrate anions.

Hydride-Containing Models for the Active Site of the Nickel−Iron Hydrogenases

The [NiFe]-hydrogenase model complex NiFe(pdt)(dppe)(CO)(3) (1) (pdt = 1,3-propanedithiolate) has been efficiently synthesized and found to be robust. This neutral complex sustains protonation to give the first nickel-iron hydride [1H]BF(4). One CO ligand in [1H]BF(4) is readily substituted by organophosphorus ligands to afford the substituted derivatives [HNiFe(pdt)(dppe)(PR(3))(CO)(2)]BF(4), where PR(3) = P(OPh)(3) ([2H]BF(4)); PPh(3) ([3H]BF(4)); PPh(2)Py ([4H]BF(4), where Py = 2-pyridyl). Variable temperature NMR measurements show that the neutral and protonated derivatives are dynamic on the NMR time scale, which partially symmetrizes the phosphine complex. The proposed stereodynamics involve twisting of the Ni(dppe) center, not rotation at the Fe(CO)(2)(PR(3)) center. In MeCN solution, 3, which can be prepared by deprotonation of [3H]BF(4) with NaOMe, is about 10(4) stronger base than is 1. X-ray crystallographic analysis of [3H]BF(4) revealed a highly unsymmetrical bridging hydride, the Fe-H bond being 0.40 Å shorter than the Ni-H distance. Complexes [2H]BF(4), [3H]BF(4), and [4H]BF(4) undergo reductions near -1.46 V vs Fc(0/+). For [2H]BF(4), this reduction process is reversible, and we assign it as a one-electron process. In the presence of trifluoroacetic acid, proton reduction catalysis coincides with this reductive event. The dependence of i(c)/i(p) on the concentration of the acid indicates that H(2) evolution entails protonation of a reduced hydride. For [2H](+), [3H](+), and [4H](+), the acid-independent rate constants are 50-75 s(-1). For [2H](+) and [3H](+), the overpotentials for H(2) evolution are estimated to be 430 mV, whereas the overpotential for the N-protonated pyridinium complex [4H(2)](2+) is estimated to be 260 mV. The mechanism of H(2) evolution is proposed to follow an ECEC sequence, where E and C correspond to one-electron reductions and protonations, respectively. On the basis of their values for its pK(a) and redox potentials, the room temperature values of ΔG(H•) and ΔG(H-) are estimated as respectively as 57 and 79 kcal/mol for [1H](+).

Asymmetric Catalytic Reactions Using P*‐Mono‐, P*,N‐ and P*,P*‐Bidentate Diamidophosphites with BINOL Backbones and 1,3,2‐Diazaphospholidine Moieties: Differences in the Enantioselectivity

AbstractA new series of P*‐chiral diamidophosphites with 1,3,2‐diazaphospholidine rings, based on (Sa)‐ or (Ra)‐BINOL and their easily accessible derivatives, has been synthesized for the first time and tested in asymmetric transition metal catalysis. Up to 99% ee was achieved in the rhodium‐catalyzed asymmetric hydrogenation of functionalized olefins and in the palladium‐catalyzed allylic substitution. The influence of the nature of the donor atoms and denticity on the asymmetric induction is discussed. In addition, the first example of a successful platinum‐catalyzed asymmetric allylic amination (up to 86% ee) with participation of organophosphorus ligands is considered.

Synthesis and complex-forming properties of thiazolyl-containing organophosphorus complexone

Alkaline hydrolysis of the previously prepared ethyl 2-methyl-2-[diethylamido-N-(4′-phenylthiazolyl-2-amido)phosphono]glycidate and 2-phenyl-2-[diethylamido-N-(4-phenylthiazolyl-2-amido)phosphono]glycidate accompanied by decarboxylation in situ of the obtained glycidic acids furnished 2-[diethylamido-(4′-phenylthiazolyl-2′-amido)phosphono]propionic and 2-phenyl-2-[diethylamido-(4′-phenylthiazolyl-2′-amido)phosphono]acetic aldehydes. The qualitative and quantitative evaluation of complex-forming ability of the compounds obtained with respect to transition metal ions was carried out. For identification of copper complex the evaluation of the stability constants of copper, cobalt, nickel, and zinc complexes was performed. Thermodynamic parameters of complex formation reactions were calculated. Correlation dependences between the physicochemical properties of metal ions and thermodynamic characteristics of complex formation with the organophosphorus ligands obtained were established.

Platinum(II) complexes of 8-quinolylmethylphosphonates: Synthesis, characterization and antitumour activity

A series of novel platinum(II) complexes of diethyl (8-dqmp) and monoethyl (8-Hmqmp) ester of 8-quinolylmethylphosphonic acid has been prepared and studied. It was shown that molecular or ionic complexes could be isolated by reaction of these organophosphorus ligands with [PtX 4] 2− (X = Cl, Br), depending on the acidity of the reaction solution. In the neutral medium diester formed dihalide adducts, trans-[Pt(8-dqmp) 2X 2] ( 1 and 2), with N-bonded ligand through the quinoline nitrogen. Under acidic conditions (pH < 3) both ligands gave the quinolinium salt complexes [LH] 2[PtX 4] ( 3 and 4, L = 8-dqmp; 7 and 8, L = 8-Hmqmp), with protonated quinoline ligand as cation and tetrahalidoplatinate complex as anion. By heating in methanol complexes 3 and 4 were converted into the corresponding dimeric hexahalidodiplatinum complexes, [8-Hdqmp] 2[Pt 2X 6] ( 5 and 6). The chelate complex [Pt(8-mqmp) 2] ( 9), with monoester ligand bonded through the quinoline nitrogen and the deprotonated phosphonic acid oxygen and forming two seven-membered {N, O} chelate rings, was obtained in neutral and basic media by reaction of platinum(II) halides either with sodium or hydrochloride salt of this monoester. The complexes were identified and characterized by elemental and thermogravimetric analyses, conductometric measurements, and by spectroscopic studies. In vitro antitumour activity of complexes was evaluated against the human epidermoid KB and murine leukaemia L1210 cell lines. These results were compared with those obtained for the palladium(II) complexes of the same phosphonate ligands and with those of platinum(II) and palladium(II) complexes of diethyl and monoethyl 2-quinolylmethylphosphonate, in order to correlate the structural and biological properties of quinoline-based aminophosphonate compounds.

New gold(I) and silver(I) complexes with organophosphorus ligands with SPNSO skeleton. Crystal and molecular structures of monomeric [Au{(SPPh 2)(O 2SR)N}(PPh 3)] (R = Me, C 6H 4Me-4) and dimeric [Ag{(SPPh 2)(O 2SPh)N}(PPh 3)] 2·2CH 2Cl 2

The reaction between gold(I) and silver(I) starting materials with anionic organophosphorus ligands of type [(SPPh 2)(O 2SR)N] − resulted in new group 11 complexes of the type [Au{(SPPh 2)(O 2SR)N}(tht)] (tht = tetrahydrothiophene), [Au{(SPPh 2)(O 2SR)N}(PPh 3)], PPN[Au{(SPPh 2)(O 2SR)N} 2] [PPN = bis(triphenylphosphine)iminium], [Ag{(SPPh 2)(O 2SR)N}] and [Ag{(SPPh 2)(O 2SR)N}(PPh 3)] (R = Me, Ph, C 6H 4CH 3-4). The new derivatives were structurally characterized by 1H and 31P NMR spectroscopy, as well as infrared and mass spectrometry. Single-crystal X-ray diffraction studies revealed monomeric structures for the gold(I) species [Au{(SPPh 2)(O 2SMe)N}(PPh 3)] ( 4) and [Au{(SPPh 2)(O 2SC 6H 4Me-4)N}(PPh 3)] ( 6), while a dimeric association was found for the silver(I) compound [Ag{(SPPh 2)(O 2SPh)N}(PPh 3)] 2·2CH 2Cl 2 ( 14·2CH 2Cl 2). The organophosphorus(V) ligand units have different coordination patterns, i.e. S-monometallic monoconnective in 4, S, O-monometallic biconnective in 6 and S, S, O-bimetallic triconnective in 14, respectively.

Rhenium(VII) polyhydrides supported by chelating bis -phosphine ligands: DPEphos, xantphos and biphep

Three new rhenium polyhydride complexes, [ReH7(L2)], incorporating bidentate organophosphorus ligands (L2 = DPEphos, xantphos and biphep), were successfully synthesized using the corresponding [ReOCl3(L2)] complexes as precursors. The polyhydride complexes were characterized by IR, 1H and 31P NMR, and elemental analysis.

Removal of Heavy Metals from Aqueous Solutions by Precipitation-Filtration Using Novel Organo-Phosphorus Ligands

An organophosphorus mixture of sodium mono- and di-(n-hexa-decyl) phosphinate was synthesized and purified, and then used as a ligand to remove heavy metals by precipitation from aqueous nitrate, chloride, and sulfate solutions. The new ligand offers more advantages over the previously studied sodium dioctyl and dodecyl phosphinates. The sodium form of the mono- and di-(n-hexa-decyl) phosphinate has a much lower solubility in water, which contributed to much lower back contamination and much lower loss of the reagent, even when excess amount of ligand was employed. Moreover, an excess amount of the ligand did not alter the filtration characteristics of the resultant precipitate. The heavy metals: lead, cadmium, mercury, cobalt, and nickel were precipitated with the sodium mono- and di-(n-hexa-decyl) phosphinate, NaL, in the form of Pb L 2(s), Cd L 2(s), Hg L 2(s), Co L 2(s), and Ni L 2(s). In the absence of free acid in the feed, a maximum removal of each metal corresponded to the stoichiometric ratio. The residual concentrations of each of the metals at the optimum conditions were measured for the different media and found to be lower than 10 ppb, lower than the acceptable levels for most regions. Lead, as a model heavy metal, was studied in more detail. Adding an acid to the feed solution reduced the removal of lead as some of the phosphinate ligand was converted to the acid form. The presence of chloride and sulfate in the feed solution; up to mole ratios to lead of 5000, and of calcium in the feed solution; up to mole ratio to lead of 200, had no effect on the removal of lead. The ligand was more selective to lead than the other four metals, and the selectivity was in the order Pb > Cd > Co & Ni > Hg. The ligand was regenerated up to 99.99% and the metals were recovered in 100 times more concentrated aqueous solutions.

Practical aspects of Lee–Goldburg based CRAMPS techniques for high-resolution 1H NMR spectroscopy in solids: Implementation and applications

Elucidating the local environment of the hydrogen atoms is an important problem in materials science. Because 1H spectra in solid-state nuclear magnetic resonance (NMR) suffer from low resolution due to homogeneous broadening, even under magic-angle spinning (MAS), information of chemical interest may only be obtained using certain high-resolution 1H MAS techniques. 1H Lee–Goldburg (LG) CRAMPS (Combined Rotation And Multiple-Pulse Spectroscopy) methods are particularly well suited for studying inorganic–organic hybrid materials, rich in 1H nuclei. However, setting up CRAMPS experiments is time-consuming and not entirely trivial, facts that have discouraged their widespread use by materials scientists. To change this status quo, here we describe and discuss some important aspects of the experimental implementation of CRAMPS techniques based on LG decoupling schemes, such as FSLG (Frequency Switched), and windowed and windowless PMLG (Phase Modulated). In particular, we discuss the influence on the quality of the 1H NMR spectra of the different parameters at play, for example LG (Lee–Goldburg) pulses, radio-frequency ( rf) phase, frequency switching, and pulse imperfections, using glycine and adamantane as model compounds. The efficiency and robustness of the different LG-decoupling schemes is then illustrated on the following materials: organo-phosphorus ligand, N-(phosphonomethyl)iminodiacetic acid [H 4pmida] [I], and inorganic–organic hybrid materials (C 4H 12N 2)[Ge 2(pmida) 2OH 2]·4H 2O [II] and (C 2H 5NH 3)[Ti(H 1.5PO 4)(PO 4)] 2·H 2O [III].