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Coordination compounds of lanthanum with carbacylamidophosphate - N,N'-tetraethyl-N''-(trichloroacetyl)phosphortriamide (HL) and 2,2'-bipyridine (bipy) of composition LaLbipy2(NO3)2 and LaL3bipy were synthesized and studied by means of X-ray, thermal gravimetric analyses, IR, and NMR spectroscopy. It was established that all the ligands in the complexes are coordinated towards lanthanum in bidentate manner. Coordination number of central ion equals ten and eight for LaLbipy2(NO3)2 and LaL3bipy, respectively. Coordination polyhedron of LaIII ion has distorted geometry between bicapped square antiprism and sphenocorona in LaLbipy2(NO3)2 and between square antiprism and triangular dodecahedron in LaL3bipy. The bonds lengths La-O and La-N are commensurate in the synthesized complexes. The both structures are characterized by the presence of numerous intermolecular interactions, which have been analyzed using Hirshfeld surface tool. A feature of the complex LaLbipy2(NO3)2 is the presence of two crystallographically independent molecules in crystal. The compounds LaLbipy2(NO3)2 and LaL3bipy are thermally stable to 175°C and 165°C, respectively. A feature of the tris-complex LaL3bipy is the presence of a phase transition at a temperature of 96°C. [ABSTRACT FROM AUTHOR]

Considering the growing interest in lanthanide‐based multifunctional materials two mixed‐ligand complexes [Ln(L)3bipy] (Ln=TbIII, DyIII) with carbacylamidophosphate (CAPh) type ligand – dimethyl‐N‐trichloroacetylamidophosphate (HL) and additional bidentate ligand 2,2'‐bipyridine (bipy) were obtained and studied by X‐ray diffraction study, thermal gravimetric analysis, and luminescence spectroscopy. The obtained complexes are monomeric and isostructural with earlier reported europium analog and crystallizes in the monoclinic system (space group C2/c). They are stable during long‐term storage for at least a couple of years as well as thermally stable up to nearly 200 °C. Both complexes exhibit f–f luminescence upon excitation into the 2,2'‐bipyridine absorption band, being emitters of green (TbIII) and yellow (DyIII) light. The luminescence intensity of the obtained complexes decreases constant exposure to UV radiation for several hours and then stays constant for at least till 32 h. [ABSTRACT FROM AUTHOR]

The tetrakis complex of neodymium(III), tetrakis{μ-N-[bis(pyrrolidin-1-yl)phosphoryl]acetamidato}bis(propan-2-ol)neodymiumsodium propan-2-ol monosolvate, [NaNd(C10H16Cl3N3O2)4(C3H8O)2]·C3H8O or NaNdPyr4(i-PrOH)2·i-PrOH, with the amide type CAPh ligand bis(N,N-tetramethylene)(trichloroacetyl)phosphoric acid triamide (HPyr), has been synthesized, crystallized and characterized by X-ray diffraction. The complex does not have the tetrakis(CAPh)lanthanide anion, which is typical for ester-type CAPh-based coordination compounds. Instead, the NdO8 polyhedron is formed by one oxygen atom of a 2-propanol molecule and seven oxygen atoms of CAPh ligands in the title compound. Three CAPh ligands are coordinated in a bidentate chelating manner to the NdIII ion and simultaneously binding the sodium cation by μ2-bridging PO and CO groups while the fourth CAPh ligand is coordinated to the sodium cation in a bidentate chelating manner and, due to the μ2-bridging function of the PO group, also binds the neodymium ion.

The samarium complexes with carbacylamidophosphate type ligand—dimethyl-N-bezoylamidophosphate and different ancillary ligands have been synthesized and their luminescence properties have been investigated. On irradiation with ultraviolet radiation the complexes display SmIII-centered intensive luminescence in visible (red–orange emission) and near-infrared spectral regions both in solid state and in non-aqueous solutions. The color coordinates, quantum yield and decay curves of the complexes are discussed in detail. Values of the emission decay times in the visible region lie in the range of 0.1–0.2 ms. It was shown that bands intensity distribution in the luminescence spectra for complexes under consideration depends on the composition of the complex and differs for the crystalline samples and the solutions. The quantum yield for the complexes solutions varies in the range 0.83–1.75%. The intramolecular energy transfer in the complexes is discussed. The obtained complexes can be considered as promising material for an emitting component of OLEDs or fluorescent markers. [ABSTRACT FROM AUTHOR]

The caesium salt of dimethyl-N-benzoylamidophosphate, namely, aqua[dimethyl (N-benzoylamido-κO)phosphonato-κO]caesium, [Cs(C9H11NO4P)(H2O)] or CsL·H2O, is reported. The compound crystallizes in the monoclinic crystal system in the P21/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoylamidophosphate anions towards the caesium cations.

The caesium salt of dimethyl-N-benzoylamidophosphate, namely, aqua[dimethyl (N-enzoylamido-O)phosphonato-O]caesium, [Cs(C9H11NO4P)(H2O)] or CsL•H2O, is reported. The compound crystallizes in the monoclinic crystal system in the P21/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoylamidophosphate anions towards the caesium cations. [ABSTRACT FROM AUTHOR]

The novel binuclear Zn(II) complex of general formula Zn2(L)4(CH3OH)2 where HL is N-[bis(benzylamino)phosphoryl]-2,2,2-trichloroacetamide has been synthesized from non-aqueous solution and characterized by elemental analysis, FTIR and NMR spectroscopy as well by X-ray single crystal diffraction. This complex represents the third example of binuclear complexes with this ligand within four known for today.

• Crystal structure of new octa-coordinated carbacylamidophosphate-la (III) complex C1. • Sonochemical synthesis of nano/micro structures of Carbacylamidophosphate-based la (III) complexes C'1 - C'3. • Study of bonding modes in the synthesized complexes via DFT. • Quantitative analyses of intermolecular interactions in the crystalline structures by hirshfeld and NCI analyses. • In vitro evaluation of antibacterial property of the synthesized compounds. The present study tries to contribute to the body of knowledge concerning the effects of O-donor ligands based on carbacylamidophosphate on the topology, geometry, and dimensions of relevant metal complexes. Accordingly, the octa-coordinated lanthanum (III) complex with formula, [La(L1) 4 Cl 2 ]Cl (C1) (L1 = 4-NC 5 H 4 C(O)NHP(O)(NC 6 H 12) 2), has been synthesized and its crystal structure has been determined. In the crystal structure, C1 is C 2 -symmetrical, and there are separate [La(L1) 4 Cl 2 ]+ cations and Cl- anions. In the complex molecule, the four L1 ligands adopt two anti - and two syn -chelating conformations. Moreover, two other carbacylamidophosphate-based lanthanide complexes La(L2) 2 (NO 3) 3 (C2) (L2 = PhC(O)NHP(O)(NH(tert ‑C 4 H 9)) 2) 2 (NO 3) and La(L3) 2 (NO 3) 3 (H 2 O)[(CH 3) 2 CO] (C3) (L3 = (4-NO 2 C 6 H 4 CONHPO(NC 4 H 8 O) 2) were considered and density functional theory computations, at the B3PW91 level, were performed to gain a deeper understanding of the structural and electronic properties in complexes (C1 - C3). Nano and micro-structures of (C'1 - C' 3) were prepared by means of a sonochemical process to study how the reaction condition and non-covalent forces function in terms of the form as well as the size of the particles in these complexes. Thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) were performed on compounds C'1- C' 3. The Hirshfeld surface analysis and NCI method were used to show the effects of non-covalent interactions on the compounds' morphologies. The antimicrobial activity of all selected compounds has been screened against two Gram-positive (Bacillus subtilis, Staphylococcus aureus) and one Gram-negative (Escherichia coli) bacteria by well diffusion method. The results indicated that all selected compounds did not show any antibacterial activity against bacteria as compared to standard drugs. [Display omitted] New octa-coordinated lanthanum (III) complex, [La(L1) 4 Cl 2 ]Cl, containing a carbacylamidophosphate ligand (L1) has been synthesized at bulk form and nano-scale. Crystal structure is observed in a butterfly geometry and nanostructures are determined in a rod-like morphology. To gain a deeper understanding of the adopted bonding modes and role of non-covalent interactions in CAPh-La (III) complexes, two other carbacylamidophosphate-based lanthanide complexes were considered, and their micro/nano-structures were prepared, as well as theoretical calculation have been executed. The antimicrobial activity of all selected compounds has been screened against some bacteria strains. [ABSTRACT FROM AUTHOR]

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[Display omitted] • The new CAPh based lanthanide complexes [Ln(NO 3)(L) 2 (bipy)] and [Ln(L) 3 (bipy)] were synthesized. • The CAPh-based europium and terbium nitrate complex crystal structures were solved. • Eu3+ and Tb3+ f-f luminescence with lifetimes 1.7–2.3 ms was observed. Two series of lanthanide coordination compounds, [Ln(NO 3)(L) 2 (bipy)] and [Ln(L) 3 (bipy)], where Ln3+ = Eu, Gd, Tb, with the carbacylamidophosphate CAPh ligand N,N,N′,N′-tetraethyl-N″-(trichloroacetyl) phosphoric triamide HL = Cl 3 CC(O)N(H)P(O)(NEt 2) 2 and α,α'-bipyridine, were synthesized. The complexes were characterized using infrared, ultraviolet diffuse reflection, and luminescence spectroscopy, as well as elemental and X-ray analyses. The bidentate coordination of the deprotonated CAPh ligand was confirmed through the analysis of the complexes' IR spectra and by X-ray analysis of the bis-CAPh Eu(III) and Tb(III) complexes. The emission and excitation solid-state spectra of the Eu(III) and Tb(III) complexes, as well as the f → f luminescence decay times, were measured at room temperature. Phosphorescence spectra of the Gd(III) complexes were measured at 77 K. The lowest ligands' triplet state energy depends on the number of coordinated CAPh ligands in the complexes. The Eu(III) and Tb(III) compounds exhibited a strong metal-centered emission with decay times ranging from 1.72 ms to 2.3 ms. Intrinsic quantum yields (QLn Ln) equal 82 % for [Eu(NO 3)(L) 2 (bipy)] and 70 % for [Eu(L) 3 (bipy)]. The Tb(III) complexes revealed a very efficient ligand-to-metal energy transfer at room temperature. [ABSTRACT FROM AUTHOR]

The reaction of HoCl3·6H2O with 2,2,2-trichloro-N-(dimorpholinophosphoryl)acetamide (carbacylamidophosphate (CAPh) type ligand, C10Cl3H8N3O4P, HL) in acetone-isopropanolic solution produces the title coordination compound [Ho(HL)2(H2O)Cl3] (1). The complex with a low for lanthanides coordination number 6 crystallizes in the triclinic space group P 1 ¯ . The unit cell parameters are a = 11.0587(11) Å, b = 14.2224(12) Å, c = 14.2520(11) Å, α = 116.192(9)°, β = 104.170(8)°, γ = 91.342 (8)°, V = 1927.8(3) Å3 and Z = 2. The HoIII ion is octahedrally coordinated by three chlorine ions, two O atoms of CAPh ligands phosphoryl groups and one O atom of water molecule. The [Ho(HL)2(H2O)Cl3] molecules are linked via Owater–H⋯Omorpholine hydrogen bonds, forming chains along [100] crystallographic direction. These chains are bound into a three-dimensional framework due to the Cmorpholine–H⋯Cl intermolecular hydrogen bonds. Hirshfeld surface analysis and two-dimensional fingerprint plots have been used to identify the intermolecular interactions presented in the crystal. The X-ray structure of hexacoordinate holmium(III) complex with the carbacylamidophosphate (CAPh) ligand 2,2,2-trichloro-N-(dimorpholinophosphoryl)acetamide (CCl3C(O)N(H)P(O)[N(CH2)4O]2) is reported and compare with the similar complex structures. Hirshfeld surface analysis employed to identify intermolecular interactions within the structure. [ABSTRACT FROM AUTHOR]

New mononuclear six-coordinate lanthanide coordination compounds [Ln (HL)3Cl3] (HL = (2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamideCCl3C(O)N(H)P(O)[N(CH2)5]2, carbacylamidophosphate (CAPh) type ligand) have been synthesized from non-aqueous solutions. The complexes have been characterized by elemental analysis, spectroscopic methods (FTIR, 1H- and 31P-NMR, UV-Vis). The structure of [Sm(HL)3Cl3] has been further confirmed by single crystal X-ray diffraction analysis.

The lanthanides coordination compounds LnL3, LnL3Phen and LnL3Dipy with bulky aryl-functionalised carbacylamidophosphate (CAPh) ligand N-(diphenylphosphoryl)benzamide (HL=PhC(O)N(H)P(O)Ph2) were synthesized for luminescent thin films producing. The films were obtained by vacuum evaporation and spin coating methods and exhibited intensive monochromatic photoemission with decay times equal to 0.78 1.34 ms.

In the title compound, C20H18NO3P, the C=O and P=O groups of the carbacylamidophosphate (CAPh) fragments are located in a synclinal position relative to each other and are pre-organized for bidentate chelate coordination of metal ions. The N—H group is involved in the formation of an intramolecular hydrogen bond. In the crystal, molecules do not form strong intermolecular interactions but the molecules are linked via weak C—H...π interactions, forming chains along [001].

[Display omitted] • New sodium and LnIII complexes with carbacylamidophosphate ligand were synthesized. • The structures, thermal stability and spectroscopy of these compounds are discussed. • The LnIII luminescence is efficiently sensitized by the ligands in the complexes. The two new sodium coordination polymers [NaL] n (1Na) and [NaL·2.5 H 2 O] n (2Na) on the base of carbacylamidophosphate type ligand diphenyl- N -trichloroacetylamidophosphate (HL, CCl 3 C(O)N(H)P(O)[OC 6 H 5 ] 2) and the two series of new lanthanide tris- and anionic tetrakis-complexes of general formulas [Ln(L) 3 phen] (1Ln ; Ln3+ = La, Nd, Eu, Tb; phen = 1,10-phenanthroline), PPh 4 [Ln(L) 4 ] (2Ln; Ln3+ = La, Nd, Eu, Tb) are reported. The obtained compounds' structural, spectroscopic, and thermal properties are discussed in detail based on X-ray diffraction data with shapes of polyhedra analysis, IR, 1H NMR, absorption and luminescence spectroscopy, and thermal gravimetric analysis. [ABSTRACT FROM AUTHOR]

Two new Chitosan-based nanocomposite films were prepared: Chitosan /7% Ag nanoparticles (NPs) (NC1) and Chitosan/7% Ag NPs/5%Carbacylamidophosphate(NC2), in which the carbacylamidophosphate derivitive is N-Nicotinyl-N′,N″- bis(hexamethylenyl) phosphorictriamide (NHE) with the formula: C5H4NC(O)NHP(O)(NC6H12)2. X-ray Powder Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM) and Energy Dispersive X-ray Spectroscopy (EDS) methods were used to characterize and confirm the prepared frameworkrs. XRD graph of the two nanocomposites showed all the characteristic peaks of NHE, Ag NPs, and chitosan, indicating the fact that the preparing process has not made any changes in the phases of the nanocomposites components. All the SEM micrographs and EDS analysis results also confirmed the desired structures. To study the effect of the additive NHE on the antibacterial activity of the films, in vitro antibacterial tests were done on the prepared nanocomposites against two Gram-positive (Staphylococcus aureus, Bacillus cereus) and two Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa) in Brain-Heart Infusion(BHI) medium. Results showed that the antibacterial effects of the nanocomposite containing NHE on each of the four bacteria is stronger than those for the nanocomposite without NHE.

In the title compound, C20H18NO3P, the C=O and P=O groups of the carbacyl­amido­phosphate (CAPh) fragments are located in a synclinal position relative to each other and are pre-organized for bidentate chelate coordination of metal ions. The N—H group is involved in the formation of an intra­molecular hydrogen bond. In the crystal, mol­ecules do not form strong inter­molecular inter­actions but the mol­ecules are linked via weak C—H···π inter­actions, forming chains along [001]. [ABSTRACT FROM AUTHOR]

Abstract Two carbacylamidophosphates ligands, 4-NC 5 H 4 C(O)NHP(O)R 2 , [where R = cyclopentylamine (L 1) and tert -butylamine (L 2)] were used to synthesize their Mn(II) complexes, C 1 and C 2. The crystal structures of the C 1 and C 2 complexes were determined by single crystal X-ray diffraction techniques. X-ray crystallography analysis revealed that C 1 and C 2 are crystallized in the monoclinic C 2/ c and P2 1 /n space groups, respectively. The results indicated that these similar ligands have different coordination patterns. Ligand L 1 acts as a bidentate bridging ligand via the oxygen atom of the phosphoryl group and the nitrogen atom of the pyridine cycle between two Mn(II), while ligand L 2 coordinates to Mn(II) via the nitrogen atom of the pyridine cycle. Quantum chemical studies were also performed to interpret two different coordination behavior of the ligands, using B3LYP/def2-TZVP level of theory. Graphical abstract Image 1 Highlights • Synthesis of two Mn(II) complexes with 4-pyridinecarbacylamidophosphate (PCAPh) ligands are reported. • Crystal structures show different coordination patterns for similar PCAPh ligands. • Theoretical studies have been used to interpret the PCAPh coordination behavior. [ABSTRACT FROM AUTHOR]

Carbacylamidophosphates are important compounds with unique physicochemical properties and many biological and chemical applications. Here, new derivatives of this class of compounds containing nicotinamide (nia), with the formula (nia)P(O)R 2 , R = NC 4 H 8 ( 1 ), NC 5 H 10 ( 2 ), NC 6 H 12 ( 3 ), 4-CH 3 -NC 5 H 9 ( 4 ), NC 4 H 8 O ( 5 ) and N(CH 3 )(C 6 H 11 ) ( 6 ), were synthesized from the reaction of N-nicotinyl phosphoramidic dichloride with various cyclic aliphatic amines. The characterization and spectroscopic study of the products were carried out by 1 H, 13 C, 31 P NMR and IR spectroscopy, and elemental analysis. For molecules 1 – 3 , with the increasing ring size of the amine groups, from five-to seven-membered, the δ ( 31 P) peaks shift downfield, 3 J (P, C) aliphatic decreases, the P O bond gets stronger and the C O bond gets weaker. The 1 H NMR spectra of compounds 2 and 6 demonstrated interesting long-range 5 J P,H or 7 J P,H coupling constants. Long-range coupling of pyridine ring protons with 4 J (H,H) = 1.6 Hz were also detected for molecule 5 . The crystal structures of compounds 2 – 4 and 6 were also determined by X-ray crystallography. The data revealed that the six-membered aliphatic rings in compounds 2 , 4 and 6 have a stable chair conformation. The phosphoryl and the carbonyl groups have anti configurations in all crystals, the phosphorus atoms in these structures have a distorted tetrahedral configuration and the environment of most nitrogen atoms is practically planar in all the structures. All the structures form dimers through strong intermolecular P O…H N hydrogen bonds. These dimers connect to each other via various electrostatic weak bonds to produce a 3-D network in each lattice. Moreover, the in vitro antibacterial activities of compounds 1 – 6 were measured for Staphylococcus aureus and Escherichia coli bacteria in nutrient agar culture medium by the disk method. The antibacterial effect of all the compounds against E. coli was very similar to that of chloramphenicol. Compound 4 showed the most activity toward both tested bacteria and its activity against E. coli was even greater than that of chloramphenicol. The growth inhibitory zone (GIZ) of the synthesized molecules for both bacteria was dependent on the substituent nature of the phosphorus atom in each compound. [ABSTRACT FROM AUTHOR]

Abstract: New coordination compounds with the formulae UO2(NO3)2(HL1)2 (A), UO2(NO3)(L1)(HL1) (B) and UO2(L2)2(HL2) (C), where HL1 =Cl3CCONHP(O)(N(CH2)5)2, HL2 =Cl3CCONHP(O)(N(Et)2)2, were synthesized and characterized by means of 1H NMR and IR spectroscopy, and X-ray diffraction analysis. It was found that in A the ambidentate HL1 ligands coordinate to the dioxouranium(VI) cations in the neutral form in a monodentate manner via the oxygen atom of the phosphoryl group, by analogy with the previously described UO2(NO3)2(HL2)2 (D), UO2(NO3)2(HL3)2 (E) and UO2(NO3)2(HL4)2 (F), where HL3 =Cl3CCONHP(O)(N(CH2)4)2 and HL4 =Cl3CCONHP(O)(N(Me)(Ph))2. In contrast, in B and C the ligands act in two modes, namely in the neutral HL1 (HL2) form with a monodentate coordination and in a deprotonated L1− (L2− ) form with a bidentate coordination via the oxygen atoms of the phosphoryl and carbonyl groups, forming six-membered chelate cycles. The extraction of the dioxouranium(VI) nitrate from HNO3 solutions using HL1, HL2 and HL3 in toluene was carried out. [Copyright &y& Elsevier]

In this work, the photo- and electroluminescence properties of new red phosphores based on europium complexes with carbacylamidophosphate (CAPh) ligands and additional aromatic ligands 1,10-phenantroline and 4,4'-bipyridine have been studied. Compounds Eu(L¹)3(phen) (1), Eu(L²)3(phen) (2), Eu2(L¹)6(i-prOH)2(4,4'-bipy) (3) and Eu2(L )6(H2O)2(4,4'-bipy) (4), where HL¹ - 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, HL² - 2,2,2-trichloro-N-(dimorpholin-1-yl-phosphoryl)acetamide, were synthesized. Technology of europium complexes coating from solutions with different concentrations in different solvents has been developed. Experimental samples of light-emitting planar heterostructures were fabricated using the device architecture comprising an anode (ITO), a hole transport layer of 1,4-Bis(diphenylamino)benzene (BDB), a layer of complex and a cathode (Al or Mg). Another heterostructure configuration with a hole-transport layer of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) has also been investigated. The different types of planar heterostructures were prepared, and their current-voltage characteristics have been discussed. [ABSTRACT FROM AUTHOR]

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt 4 [LnL 4 ] (Ln 3+ =La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes. The effect of changing the alkali metal counterion to the organic cation NEt 4 + on the structure and properties of the tetrakis-complex [LnL4] - is analyzed. The complexes exhibit bright characteristic for respective lanthanides luminescence. Rather high intensity of the band of 5 D 0 → 7 F 4 transition, observed in the luminescence spectrum of NEt 4 [EuL 4 ], is discussed based on theoretical calculations., (© 2022 Wiley-VCH GmbH.)

Abstract: Three new carbacylamidophosphates with formula CH n Cl3−n C(O)NHP(O)(NHCH(CH3)2)2 (n = 2 (1); n = 1 (2); n = 0 (3)) and their organotin compounds with formula (1)SnCl2Me2(μ-1)SnCl2Me2 (4), SnCl2Me2(2)2·C6H5CH3 (5) and [SnCl2Me2(3)] n (6) were synthesized and characterized by elemental, IR and NMR spectra analyses. The spectroscopic properties of complexes were compared with those corresponding ligands. The crystal structures of complexes were determined by X-ray crystallography, which reveals that complex 4 is binuclear structure with two non-equivalent Sn atoms. One adopts a distorted trans(C,C) cis(OP,OP) cis(Cl,Cl) octahedral configuration, while the other adopts a distorted trigonal bipyramidal geometry composed of two methyl groups, two chlorine atoms and carbonyl group. Molecule 5 is centrosymmetric with two OP, disordered chlorine and methyl groups in trans positions. Toluene molecules are located in the interlayer spaces of 5. In compound 6, bonding via both PO and CO functionalities forms 1D infinite chain structures along b axis. The Sn–OP bond length in 6 is significantly longer than the same distance in 4 and 5, while the O#x2013;Cl bonds are shorter. The bond lengths in these complexes were compared with those of N-benzoyl carbacylamidophosphates. [Copyright &y& Elsevier]

Abstract: Coordination compounds with general formula [Ln(L1)3phen], where Ln=Nd, Eu, Er, Yb, HL1 =N,N′-dipyrrolidine-N′′-trichloracetylphosphortriamide, phen=1,10-phenanthroline; [Ln(L1)3bpm], where Ln=La, Nd, Eu, Gd, Er, Y, bpm=2,2′-bipyrimidine and [{Ln(L2)3}2(μ-bpm)], where Ln=La, Nd, Eu, Gd, Er, Y, HL2 =dimethyl-N-trichloracetylamidophosphate have been synthesized and characterized by means of IR and UV–Vis spectroscopy. Crystal structures of [Nd(L1)3phen] (1), [Nd(L1)3bpm] (2) and [{Nd(L2)3}2(μ-bpm)] (3) have been determined. It was found, that in the deprotonated form the phosphoryl ligands (L1)− and (L2)− are coordinated to the neodymium atoms in a bidentate manner via the oxygen atoms of the phosphoryl and the carbonyl groups with formation of six-membered metallocycles. In the case of compounds 1 and 2 the 1,10-phenanthroline (or 2,2′-bipyrimidine) molecules are coordinated to the metals in a bidentate manner via the nitrogen atoms. In contrast 2,2′-bipyrimidine acts in the bidentate-bridge mode forming binuclear complex 3. Variable-temperature magnetic susceptibility measurements of 3 and [{Gd(L2)3}2(μ-bpm)] (4) reveal a weak antiferromagnetic interaction between the two magnetic centres, whereas in the case of [{Eu(L2)3}2(μ-bpm)] (5) the presence of spin–orbit coupling leads to a deviation from the Curie and Curie–Weiss laws. [Copyright &y& Elsevier]

Twenty new carbacylamidophosphates R′2P(O)NHC(O)R, where R=acetyl and benzoyl derivatives, R′=3, 5, 6 and 7 membered ring amines, were synthesized and characterized by IR, 1H, 13C and 31P NMR spectroscopy, and elemental analysis. The crystal structures of CCl3C(O)NHP(O)[N(C5H10)]2 (1d), CHCl2C(O)NHP(O)[N(C5H10)]2 (2d), Cl–C6H4C(O)NHP(O)[NH(C5H9)]2 (5b) and Cl–C6H4C(O)NHP(O)[N(C4H8)O]2 (5e) have been determined. All four compounds indicate the formation of intermolecular –PH–N– hydrogen bonds which give dimeric aggregates. They were centrosymmetric in 5b and 5e. Also, the mass spectra of these compounds, in addition to our previously synthesized 29 carbacylamidophosphates, were recorded and the observed fragmentation behaviors were studied. The main pathways of fragmentation of N-acetyl and N-benzoyl phosphoric amide derivatives indicated that the molecular ions involve mainly a radical cationic center at the carboxyl oxygen. All the N-benzoyl and N-acetyl phosphoramidates rearranged to the O-phosphorylated benz- or acetamides, and those readily lost the (R′)2PO2 · radicals and yielded N-protonated nitrilium ions R–C ≡ NH+ and ... The greater intensities for the ... ions in the N-benzoyl derivatives relative to R–C ≡NH+ for the N-acetyl derivatives may due to differences in the P=O,P–Namide and C–Namide bond lengths and their different specific properties in the parent molecules. [Copyright &y& Elsevier]

Abstract: Using phosphorus pentachloride as a substrate, a new carbacyclamidophosphate, N,N″-bis (2,6-dimethylmorpholino), N″-dichloroacetyl phosphoric triamide (1) has been synthesized and characterized by 1H, 31P and 13C NMR, IR spectroscopy and elemental analysis. Due to the presence of methyl disubstituted morpholine rings and the dichloroacetamide group, several conformers can be considered for this molecule. The 31P{1H} NMR spectra for the isomeric mixture of synthesized compound showed four signals with the ratio 67.1; 19.0; 12.2; 1.7, which indicates four independent conformers. The 1H NMR spectra confirmed these results. The conformational space and the molecular geometry of the molecule in the gaseous phase have been studied using the B3LYP method of approximation, with 6-31G and 6-311++G∗∗ basis sets. [Copyright &y& Elsevier]

Abstract: N,N′-bis(pyrolidino), N″-trichloroacetyl phosphoric triamide, the new carbacyclamidophospate, was synthesized and its crystal structure has been determined by X-ray single crystal diffraction analysis. The crystal structure showed two independent conformers A and B. This compound produced dimmeric aggregate due to hydrogen bonding. The compound crystallizes in orthorhombic space group Pbca with a=12.033(2)Å; b=20.148(3)Å; c=24.876(3)Å; V=6030.7(13) (Å)3, Z=8; and D=1.538mg/m3. The structure was solved by direct methods and refined to R=0.0657 and wR 2=0.1415 by full matrix anisotropic least-squares methods. The molecular geometry and vibrational frequencies of the compound in the ground state have been calculated using the Hartree-Fock with HF/6-31+G* and HF/6-311++G** and density functional method (B3LYP) with B3LYP/6-31+G* and B3LYP/6-311++G** basis set. The optimized bond lengths and bond angles are show better agreement with the experimental values by RHF/6-311++G** method. The conformer A is approximately 6kcal/mol more stable than conformer B. The energy profile was calculated for more stable structure, conformer A, by RHF/6-31+G* method as a function of θ° [O(1)–P(1)–N(3)–C(9)]. The harmonic vibrations computed of this compound by the RHF and DFT methods are in a good agreement with the observed IR spectral data. [Copyright &y& Elsevier]

Carbacylamidophosphates with the general formula RC(O)NHP(O)R1R2 constitute organophosphorus compounds that are used as insecticides, pesticides and ureas inhibitors. In this work, we studied the inhibition potency of CCl3 C(O)NHP(O)Cl21, CHCl2C(O)NHP(O)Cl22, CH2ClC(O)NHP(O)Cl23 and CF3C(O)NHP(O)Cl24, which are the major intermediates for carbacylamidophosphates synthesis towards human erythrocyte acetylcholinesterase (hAChe) activity using Ellman's modified kinetic method. Unexpectedly, it was observed that they were not only hydrolytically unstable but also inhibited hAChE in a similar manner to that produced by organophosphorus insecticides. Enzymatic data, bimolecular inhibition rate constants (ki) and IC50 values for inhibition of hAChE demonstrated that they are irreversible inhibitors and the inhibition potency of compound 2 (IC50 = 88 µM) was the greatest in comparison with compounds 1, 3 and 4. Also the electropositivity of the phosphorus atom and the hydrophobicity of the compounds demonstrated that these two factors play an additional effect and different role in the inhibitory activity of these compounds. Hydrolytic stability of the compounds was determined by Zip NMR monitoring of the loss of the parent molecules with D20 as a function of time. This study considers antiacetylcholinesterase activity according to the structural and the electronic aspects of compounds 1 4, according to IR, ¹H, 13C and 31P NMR spectral data. [ABSTRACT FROM AUTHOR]