Synthesis of 4-(4-Methylsulfonylphenyl)-3-phenyl-2(3H)-thiazole Thione Derivatives as New Potential COX-2 Inhibitors

Synthesis of novel 4-（4-methylsulfonylphenyl）-3-phenyl-2（3H）-thiazole thione derivatives with functionalized diarylheterocycle pharmacophore as potential COX-2 inhibitors was described. The title compounds were synthesized by cyclocondensation of corresponding dithiocarbamate and 2-bromo-1-（4-methylsulfonylphenyl）ethanone, followed by dehydration with H2SO4. All of the target compounds were characterized by ^1H NMR, IR and mass spectral data.     

Protonierung des 1,1,3,3,5,5‐Hexakis(dimethylamino)λ5‐[1,3,5]triphosphinins. Cyclotrimethylentriphosphinsäure. NMR‐Daten,Kristallstrukturen und quantenchemische Rechnungen

Protonation of 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ⁵‐[1,3,5]triphosphinine. Cyclotrimethylenetriphosphinic Acid. NMR Data, Crystal Structures, and Quantum Chemical Calculations Preparation of 1,1,3,3,5,5‐hexakis(dimethylamino)‐1,2‐dihydro‐3λ⁵,5λ⁵‐[1,3,5]triphosphininium‐tetrafluoroborate ( 3 ) und 1,1,3,3,5,5‐hexakis(dimethylamino)‐λ⁵‐[1,3,5]triphosphinanetriium‐tris(tetrafluoroborate) ( 4 ) from 1,1,3,3,5,5‐hexakis(dimethylamino)‐1λ⁵,3λ⁵,5λ⁵‐triphosphinine 1 and HBF₄ · O(C₂H₅)₂ are described. The structures of 3 und 4 are elucidated by n. m. r. and X‐ray structural analyses. By hydrolysis of 4 with conc. hydrochloric acid 1,3,5‐trioxo‐1λ⁵,3λ⁵,5λ⁵‐[1,3,5]triphosphinane‐1,3,5‐triol (cyclotrimethylene‐triphosphinic acid) ( 8 ) is formed. Neutralisation with NaOH yields its sodium salt 9 . 8 and 9 are characterized by their n. m. r. spectra. Quantum chemical calculations have been investigated for the compounds 1 ′– 4 ′ and the trianion 9 . The systems 1 ′– 4 ′ are distinguished from 1 – 4 by the size of the ligands at phosphorus which is reduced from N(CH₃)₂ to NH₂, respectively. The aims of the calculations are to elucidate hybridisations and molecular structures, Lewis or resonance structures, electronic charge distributions and NMR chemical shifts.     

Investigation of Some Functionalization Reactions of 4‐Benzoyl‐5‐phenyl‐1‐(4‐methoxyphenyl)‐1H‐pyrazole‐3‐carbonyl Chloride and Their Antimicrobial Activity

The 1H‐pyrazole‐3‐carboxylic acid 1 was converted via reactions of its acid chloride 3 with various asymmetrical disubstituted urea and alcohol derivatives into the corresponding novel 4‐benzoyl‐N‐(N′,N′‐dialkylcarbamyl)‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxamide 4a , b and alkyl 4‐benzoyl‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxylate 7a‐c , respectively, in good yields (57%‐78%). Friedel‐Crafts reactions of 3 with aromatic compouns for 15 min.‐2 h led to the formation of the 4‐3‐diaroyl‐1‐(4‐hydroxyphenyl)‐5‐phenyl‐1H‐pyrazoles 9a‐c , 4‐benzoyl‐1‐(4‐methoxyphenyl)‐3‐aroyl‐5‐phenyl‐1H‐pyrazoles 10a , b and than from the acylation reactions of 9a‐c were obtained the 3,4‐diaroyl‐1‐(4‐acyloxyphenyl)‐5‐phenyl‐1H‐pyrazoles 13a‐d . The structures of all new synthesized compounds were established by NMR experiments such as ¹H, and ¹³C, as well as 2D COSY and IR spectroscopic data, and elemental analyses. All the compounds were evaluated for their antimicrobial activities (agar diffusion method) against eight bacteria and two yeasts.     

Pinacol Rearrangement of 3,4‐Dihydro‐3,4‐dihydroxyquinolin‐2(1H)‐ones: An Alternative Pathway to Viridicatin Alkaloids and Their Analogs

3‐Alkyl/aryl‐3‐hydroxyquinoline‐2,4‐diones were reduced with NaBH₄ to give cis‐3‐alkyl/aryl‐3,4‐dihydro‐3,4‐dihydroxyquinolin‐2(1H)‐ones. These compounds were subjected to pinacol rearrangement by treatment with concentrated H₂SO₄, resulting in 4‐alkyl/aryl‐3‐hydroxyquinolin‐2(1H)‐ones. When a benzyl (Bn) group was present in position 3 of the starting compound, its elimination occurred during the rearrangement, and the corresponding 3‐hydroxyquinolin‐2(1H)‐one was formed. The reaction mechanisms are discussed for all transformations. All compounds were characterized by IR, ¹H‐ and ¹³C‐NMR spectroscopy, as well as mass spectrometry.     

1H, 13C and 15N NMR spectroscopic characterization of unexpected degradation products of the nifedipine analogue bis(2‐cyanoethyl) 2,6‐dimethyl‐4‐(2‐nitrophenyl)‐1,4‐dihydro‐3,5‐pyridinedicarboxylate

In the course of saponification experiments with bis(2‐cyanoethyl) 2,6‐dimethyl‐4‐(2‐nitrophenyl)‐1,4‐dihydro‐3,5‐pyridinedicarboxylate ( 1 ), an analogue of the calcium channel blocker nifedipine, three unexpected degradation products were isolated. The compounds were identified as 3‐(2‐acetamido‐1‐carboxy‐1‐propenyl)‐1‐hydroxy‐2‐indolecarboxylic acid ( 3 ), 9‐hydroxy‐1,3‐dimethyl‐β‐carboline‐4‐carboxylic acid ( 4 ) and 6‐hydroxy‐2,4‐dimethyl‐5‐oxo‐5,6‐dihydrobenzo[c][2,7]naphthyridine‐1‐carboxylic acid ( 6 ). The structures of these compounds were deduced from one‐ and two‐dimensional ¹H, ¹³C and natural abundance ¹⁵N NMR experiments (¹H,¹H‐COSY, gs‐HSQC, gs‐HMBC, ¹⁵N gs‐HMBC), and corroborated by comparison of their NMR data with the respective data for structurally similar compounds. Copyright © 2002 John Wiley & Sons, Ltd.     

Preparation,Structural Characterization,and Antifungal Activities of Complexes of Group 12 Metals with 2‐Acetylpyridine‐ and 2‐Acetylpyridine‐N‐oxide‐4N‐phenylthiosemicarbazones

Reaction of group 12 metal dihalides in ethanolic media with 2‐acetylpyridine ⁴N‐phenylthiosemicarbazone ( H4PL ) and 2‐acetylpyridine‐N‐oxide ⁴N‐phenylthiosemicarbazone ( H4PLO ) afforded the compounds [M(H4PL)X₂] (X = Cl, Br, M = Zn, Cd, Hg; X = I, M = Zn, Cd) ( 1–8 ), [Hg(4PL)I]₂ ( 9 ) and [M(H4PLO)X₂] (X = Cl, Br, I, M = Zn, Cd, Hg) ( 10–18 ). H4PL , H4PLO and their complexes were characterized by elemental analysis and by IR and ¹H and ¹³C NMR spectroscopy (and the cadmium complexes by ¹¹³Cd NMR spectroscopy), and H4PL , H4PLO , ( 5 · DMSO) and ( 9 ) were additionally studied by X‐ray diffraction. H4PL is N,N,S‐tridentate in all its complexes, including 9 , in which it is deprotonated, and H4PLO is in all cases O,N,S‐tridentate. In all the complexes, the metal atoms are pentacoordinate and the coordination polyhedra are redistorted tetragonal pyramids. In assays of antifungal activity against Aspergillus niger and Paecilomyces variotii, the only compound to show any activity was [Hg(H4PLO)I₂] ( 18 ).     

Reductive Coupling Reaction of Aryliminomethylferrocenes with Triethyl Orthoformate Induced by Low‐valent Titanium

Reductive coupling reaction of aryliminomethylferrocenes FcCH = NAr[(1, Ar=QHs (a), p‐ClC₆H₄ (b), p‐BrC₆H₄ (c), p‐CH₃C₆H₄ (d), m‐ClC₆H₄ (e)] with triethyl orthoformate (2) in Zn‐TiCl₄ system gave three kinds of products: 1, 3‐diaryl‐4, 5‐diferrocenyl imidazolidines (3), N, N‐disubstituted formamides (4), and 1, 2‐diferrocenyl ethylene (5). ¹H NMR spectra proved that all the compounds 3 obtained were dl‐isomers. All the new compounds 3 and 4 were characterized by elemental analysis, ¹H NMR, ¹³C NMR (for 3) and IR spectra. The molecular structure of 3c was determined by X‐ray diffraction.     

Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

The anionic gold(I) complexes [1‐(Ph₃PAu)‐closo‐1‐CB₁₁H₁₁]^? ( 1 ), [1‐(Ph₃PAu)‐closo‐1‐CB₉H₉]^? ( 2 ), and [2‐(Ph₃PAu)‐closo‐2‐CB₉H₉]^? ( 3 ) with gold–carbon 2c–2e σ bonds have been prepared from [AuCl(PPh₃)] and the respective carba‐closo‐borate dianion. The anions have been isolated as their Cs⁺ salts and the corresponding [Et₄N]⁺ salts were obtained by salt metathesis reactions. The salt Cs‐ 3 isomerizes in the solid state and in solution at elevated temperatures to Cs‐ 2 with ΔH_iso=(?75±5) kJ mol^?1 (solid state) and ΔH^≠=(118±10) kJ mol^?1 (solution). The compounds were characterized by vibrational and multi‐NMR spectroscopies, mass spectrometry, elemental analysis, and differential scanning calorimetry. The crystal structures of [Et₄N]‐ 1 , [Et₄N]‐ 2 , and [Et₄N]‐ 3 were determined. The bonding parameters, NMR chemical shifts, and the isomerization enthalpy of Cs‐ 3 to Cs‐ 2 are compared to theoretical data.     

Reaction of 3‐Hydroxyquinoline‐2,4‐diones with Isocyanates and Thermally Induced Transformation of the Reaction Products

3‐Hydroxyquinoline‐2,4‐diones 1 react with isocyanates to give novel 1,2,3,4‐tetrahydro‐2,4‐dioxoquinolin‐3‐yl (alkyl/aryl)carbamates 2 and/or 1,9b‐dihydro‐9b‐hydroxyoxazolo[5,4‐c]quinoline‐2,4(3aH,5H)‐diones 3 . Both of these compounds are converted, by boiling in cyclohexylbenzene solution in the presence of Ph₃P or 4‐(dimethylamino)pyridine, to give 3‐(acyloxy)‐1,3‐dihydro‐2H‐indol‐2‐ones 8 . All compounds were characterized by IR, and ¹H‐ and ¹³C‐NMR spectroscopy, as well as by EI mass spectrometry.     

Antioxidative vs cytotoxic activities of organotin complexes bearing 2,6‐di‐tert‐butylphenol moieties

Two series of organotin(IV) complexes with Sn–S bonds on the base of 2,6‐di‐tert‐butyl‐4‐mercaptophenol ( L ¹ SH ) of formulae Me₂Sn(L¹S)₂ ( 1 ); Et₂Sn(L¹S)₂ ( 2 ); Bu₂Sn(L¹S)₂ ( 3 ); Ph ₂ Sn(L¹S)₂ ( 4 ); (L¹)₂Sn(L¹S)₂ ( 5 ); Me₃Sn(L¹S) ( 6 ); Ph₃Sn(L¹S) ( 7 ) (L¹ = 3,5‐di‐tert‐butyl‐4‐hydroxyphenyl), together with the new ones [Me₃SnCl(L²)] ( 8 ), [Me₂SnCl₂(L²)₂] ( 9 ) ( L ²  = 2‐(N‐3′,5′‐di‐tert‐butyl‐4′‐hydroxyphenyl)‐iminomethylphenol) were used to study their antioxidant and cytotoxic activity. Novel complexes 8 , 9 of Me_nSnCl_4 ? n (n = 3, 2) with Schiff base were synthesized and characterized by ¹H, ¹³C NMR, IR and elemental analysis. The crystal structures of compounds 8 and 9 were determined by X‐ray diffraction analysis. The distorted tetrahedral geometry around the Sn center in the monocrystals of 8 was revealed, the Schiff base is coordinated to the tin(IV) atom by electrostatic interaction and formation of short contact Sn–O 2.805 Å. In the case of complex 9 the distorted octahedron coordination of Sn atom is formed. The antioxidant activity of compounds as radical scavengers and reducing agents was proved spectrophotometrically in tests with stable radical DPPH, reduction of Cu²⁺ (CUPRAC method) and interaction with superoxide radical‐anion. Moreover, compounds have been screened for in vitro cytotoxicity on eight human cancer cell lines. A high activity against all cell lines with IC₅₀ values 60–160 nM was determined for the triphenyltin complex 7 , while the introduction of Schiff base decreased the cytotoxicity of the complexes. The influence on mitochondrial potential and mitochondrial permeability for the compounds 8 and 9 has been studied. It is shown that studied complexes depolarize the mitochondria but don't influence the calcium‐induced mitochondrial permeability transition.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Synthesis and Characterization of β‐Diketiminate Aluminum Compounds and Their Use in the Ring‐Opening Polymerization of ε‐Caprolactone

Four aluminum alkyl compounds, [CH{(CH₃)CN‐2,4,6‐MeC₆H₂}₂AlMe₂] ( 1 ), [CH{(CH₃)CN‐2,4,6‐MeC₆H₂}₂AlEt₂] ( 2 ), [CH{(CH₃)CN‐2‐iPrC₆H₄}₂AlMe₂] ( 3 ), and [CH{(CH₃)CN‐2‐iPrC₆H₄}₂AlEt₂] ( 4 ), bearing β‐diketiminate ligands [CH{(Me)CN‐2,4,6‐MeC₆H₂}]₂ (L¹H) and [CH{(Me)CN‐2‐ⁱPrC₆H₄}]₂ (L²H) were obtained from the reactions of trimethylaluminum, triethylaluminum with the corresponding β‐diketiminate, respectively. All compounds were characterized by ¹H NMR and ¹³C NMR spectroscopy, single‐crystal X‐ray structural analysis, and elemental analysis. Compounds 1 – 4 were found to catalyze the ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) with good activity.     

N‐Silylaminotitanium Chlorides — Synthesis,Structures, Multinuclear Magnetic Resonance,and some Applications

N‐Silylaminotitanium trichlorides, Me₃S(R)N‐TiCl₃ ( 18 ) [R = ^tBu ( a ), SiMe₃ ( b ), 9‐borabicyclo[3.3.1]nonyl (9‐BBN)( c )], and (CH₂SiMe₂)₂N‐TiCl₃ ( 18d ) were obtained in high yield and high purity from the reaction of the respective bis(silylamino)plumbylene with an excess of titanium tetrachloride. The crystal structure of 18a was determined by X‐ray analysis. The reactions of the analogous stannylenes with an excess of TiCl₄ did not lead to 18 . N‐Lithio‐trimethylsilyl[9‐(9‐borabicyclo[3.3.1]nonyl)]amine ( 8 ) was prepared, structurally characterized and used for the synthesis of a new bis(amino)stannylene 10 and a plumbylene 11 . The compounds 18a—d served as ideal starting materials for the synthesis of bis(silylamino)titanium dichlorides, where the silylamino groups can be identical ( 19 ) or different ( 20 ). This was achieved either by the reaction of 18 again with bis(amino)plumbylenes or with lithium N‐silylamides. In contrast to the direct synthesis starting from titanium tetrachloride and two equivalents of the respective lithium amide, which in general affords 19 with identical amino groups only in low yield, the procedure starting from 18 is much more versatile and gave the pure compounds 19 or 20 in almost quantitative yield. Further treatment of the dichlorides 19 or 20 with lithium amides led to tris(amino)titanium chlorides 21 . The dichlorides 19 or 20 reacted with two equivalents of alkynyllithium reagents to give the first well characterized examples of di(alkyn‐1‐yl)bis(N‐silylamino)titanium compounds 22 — 27 . These compounds reacted with trialkylboranes (triethyl or tripropylborane) by 1, 1‐organoboration. In some cases, the extremely reactive reaction products could be identified as novel 1, 1‐bis(silylamino)titana‐2, 4‐cyclopentadienes 28 — 31 bearing a dialkylboryl group in 3‐position. In solution, the proposed structures of all products were deduced from a consistent set of data derived from multinuclear magnetic resonance spectroscopy (¹H, ¹¹B, ¹³C, ¹⁴N, ¹⁵N, ²⁹Si, ³⁵Cl NMR).     

Synthesis,structure and in vitro cytotoxicity testing of some 2‐aroylbenzofuran‐3‐ols

Five 2‐aroyl‐5‐bromobenzo[b]furan‐3‐ol compounds (two of which are new) and four new 2‐aroyl‐5‐iodobenzo[b]furan‐3‐ol compounds were synthesized starting from salicylic acid. The compounds were characterized by mass spectrometry and ¹H NMR and ¹³C NMR spectroscopy. Single‐crystal X‐ray diffraction studies of four compounds, namely, (5‐bromo‐3‐hydroxybenzofuran‐2‐yl)(4‐fluorophenyl)methanone, C₁₅H₈BrFO₃, (5‐bromo‐3‐hydroxybenzofuran‐2‐yl)(4‐chlorophenyl)methanone, C₁₅H₈BrClO₃, (5‐bromo‐3‐hydroxybenzofuran‐2‐yl)(4‐bromophenyl)methanone, C₁₅H₈Br₂O₃, and (4‐bromophenyl)(3‐hydroxy‐5‐iodobenzofuran‐2‐yl)methanone, C₁₅H₈BrIO₃, were also carried out. The compounds were tested for their in vitro cytotoxicity on the four human cancer cell lines KB, Hep‐G2, Lu‐1 and MCF7. Six compounds show good inhibiting abilities on Hep‐G2 cells, with IC₅₀ values of 1.39–8.03 µM.     

Synthesis of Some New 2‐Oxo‐N‐[(10H‐phenothiazin‐10‐yl)alkyl] Derivatives of Azetidine‐1‐carboxamides

The synthesis of a new series of 4‐aryl‐3‐chloro‐2‐oxo‐N‐[3‐(10H‐phenothiazin‐10‐yl)propyl]azetidine‐1‐carboxamides, 4a – 4m , is described. Phenothiazine on reaction with Cl(CH₂)₃Br at room temperature gave 10‐(3‐chloropropyl)‐10H‐phenothiazine ( 1 ), and the latter reacted with urea to yield 1‐[3‐(10H‐phenothiazin‐10‐yl)propyl]urea ( 2 ). Further reaction of 2 with several substituted aromatic aldehydes led to N‐(arylmethylidene)‐N′‐[3‐(phenothiazin‐10‐yl)propyl]ureas 3a – 3m , which, on treatment with ClCH₂COCl in the presence of Et₃N, furnished the desired racemic trans‐2‐oxoazetidin‐1‐carboxamide derivatives 4a – 4m . The structures of all new compounds were confirmed by IR, and ¹H‐ and ¹³C‐NMR spectroscopy, FAB mass spectrometry, and chemical methods.     

Palladium(II) Complexes of the Thiosemicarbazone and N‐Ethylthiosemicarbazone of 3‐Hydroxypyridine‐2‐carbaldehyde: Synthesis,Properties, and X‐Ray Crystal Structure

Two novel, stable Pd^II complexes, compounds 3 and 4 , of two 3‐hydroxypyridine‐2‐carbaldehyde thiosemicarbazones, 1 and 2 , resp., were prepared from Li₂PdCl₄. The single‐crystal X‐ray structure of complex 3 (= [Pd( 2 )Cl]) shows that the ligand monoanion coordinates in a planar conformation to the metal via the pyridyl N‐, the imine N‐, and the thiolato S‐atoms. Intermolecular H‐bonds, π–π, and CH ? ? ? π interactions lead to a two‐dimensional supramolecular assembly. The electronic, IR, UV/VIS, and NMR spectroscopic data of the two complexes are reported, together with their electrochemical properties. A sophisticated experimental procedure was used to determine the multiple dissociation constants of the ligands 1 and 2 by UV/VIS titration.     

Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

Zinc(II) and Cadmium(II) Complexes of the 3‐(2‐Pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) Ligand,Structural Studies of [Zn(PDPT)2Cl(ClO4)] and [Cd(PDPT)2(NO3)(ClO4)]

Two new mixed‐anion zinc(II) and cadmium(II) complexes of 3‐(2‐pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine (PDPT) ligand, [Zn(PDPT)₂Cl(ClO₄)] and [Cd(PDPT)₂(NO₃)(ClO₄)], have been synthesized and characterized by elemental analysis, IR‐ and ¹H NMR spectroscopy. The single crystal X‐ray analyses show that the coordination number in these complexes is six with four N‐donor atoms from two “PDPT” ligand and two of the anionic ligands, ZnN₄ClO_perchlorate, CdN₄O_nitrateO_perchlorate. Self‐assembly of these compounds in the solid state via π–π‐stacking interactions is discussed.     

Five Coordinated Zinc(II) and Tris‐Chelate Cadmium(II) Complexes with 2,2′‐Diamino‐5,5′‐dimethyl‐4,4′‐bithiazole – Syntheses,Spectroscopic Characterization,and Crystal Structure

The new synthesized ligand (DADMBTZ = 2,2′‐diamino‐5,5′‐dimethyl‐4,4′‐bithiazole), which is mentioned in this text, is used for preparing the two new complexes [Zn(DADMBTZ)₃](ClO₄)₂. 0.8MeOH.0.2H₂O ( 1 ) and [Cd(DADMBTZ)₃](ClO₄)₂ ( 2 ). The characterization was done by IR, ¹H, ¹³C NMR spectroscopy, elemental analysis and single crystal X‐ray determination. In reaction with DADMBTZ, zinc(II) and cadmium(II) show different characterization. In 2 , to form a tris‐chelate complex with nearly C₃ symmetry for coordination polyhedron, DADMBTZ acts as a bidentate ligand. In 1 , this difference maybe relevant to small radii of Zn²⁺ which make one of the DADMBTZ ligands act as a monodentate ligand to form the five coordinated Zn²⁺ complex. In both 1 and 2 complexes the anions are symmetrically different. 1 and 2 complexes form 2‐D and 3‐D networks via N‐H···O and N‐H···N hydrogen bonds, respectively.     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.