PNPP Hydrolysis Catalyzed by Manganese(III) Complexes with Crowned Salicylaldimine Schiff Base Ligand

Four manganese(III) complexes (MnL¹Cl, MnL²Cl, MnL⁴₂Cl, MnL⁵₂Cl) with a crowned salicylaldimine Schiff base ligand have been synthesized and employed as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (PNPP). The kinetics and mechanism of catalytic PNPP hydrolysis have been investigated. The kinetic mathematical model of PNPP cleavage catalyzed by these complexes has been proposed. The effects of the ligand structure and crown ether ring in complexes, and the reactive temperature on the rate of catalytic PNPP hydrolysis have been also examined. The results show that compared with the crown-free analogous MnL³Cl and MnL⁶₂Cl, the crowned Schiff base manganese(III) complexes, MnL¹Cl, MnL²Cl, MnL⁴₂Cl and MnL⁵₂Cl, exhibit more high catalytic activity, which follow the order: MnL¹Cl >MnL²Cl >MnL⁴₂Cl >MnL⁵₂Cl >MnL³Cl >MnL⁶₂Cl; the pseudo-first-order-rate (k_obs) for the PNPP hydrolysis catalyzed by the complex MnL¹Cl containing three crown ether rings is highest among six complexes and is 1.81 times that of MnL³Cl, 1.49 × 10³ times that of spontaneous hydrolysis of PNPP, respectively, at pH = 7.00, [S] = 2.0 × 10⁻⁴ mol dm⁻³.     

Mixed ligand complexes with 2-piperidine-carboxylic acid as primary ligand and ethylene diamine, 2,2′-bipyridyl, 1,10-phenanthroline and 2(2′-pyridyl)quinoxaline as secondary ligands: preparation,characterization and biological activity

Synthesis procedures are described for the new stable mixed ligand complexes, [Pd(Hpa)(pa)]Cl, [Pd(pa)(H₂O)₂]Cl, [Pd(pa)(en)]Cl, [Pd(pa)(bpy)]Cl, [Pd(pa)(phen)Cl], [Pd(pa)(pyq)Cl], cis-[MoO₂(pa)₂], [Ag(pa)(bpy)], [Ag(pa)(pyq)], trans-[UO₂(pa)(pyq)](BPh₄) and [ReO(PPh₃)(pa)₂]Cl (Hpa = 2-piperidine-carboxylic acid, en = ethylene diamine, bpy = 2,2′-bipyridyl, phen = 1,10-phenanthroline, pyq = 2(2′-pyridyl)quinoxaline). Their elemental analyses, conductance, thermal measurements, Raman, IR, electronic, ¹H-n.m.r. and mass spectra have been measured and discussed. 2-Piperidine-carboxylic acid and its palladium complexes have been tested as growth inhibitors against Ehrlich ascites tumour cells (EAC) in Swiss albino mice.     

Synthesis and crystal structure of Mn(II) complexes with novel macrocyclic Schiff-base ligands containing piperazine moiety

A series of Mn(II) macrocyclic Schiff-base complexes [MnLⁿCl]⁺ (n = 1–4) have been prepared via the Mn(II) templated [1+1] cyclocondensation of 2,6-diacetylpyridine or 2,6-pyridinedicarbaldehyde with the symmetrical 1,4-bis(3-aminopropyl)piperazine or the novel asymmetrical N,N′(2-aminoethyl)(3-aminopropyl)piperazine linear amines containing piperazine moiety. The complexes have been characterized by elemental analyses, IR, FAB-MS, magnetic studies and conductivity measurements. The crystal structure of [MnL²(CH₃OH)Cl](ClO₄) and [MnL⁴Cl](PF₆) complexes have also been determined showing the metal ion in a N₄OCl pentagonal bipyramidal or N₄Cl highly distorted octahedral geometry, respectively.     

Tripropylarsane Complexes of Palladium(II) and Platinum(II) — Syntheses,Spectroscopy, and Structures

Several palladium(II) and platinum(II) complexes of tripropylarsanes (AsR₃; R = Pr, iPr) with the formulae, [MCl₂(AsR₃)₂], [M₂Cl₂(μ‐Cl)₂(AsR₃)₂], [Pd₂Me₂(μ‐Cl)₂(AsR₃)₂], [Pd₂X₂(μ‐Pz)₂(AsR₃)₂] (X = Cl or Me, Pz = pyrazolate), [Pd₂Cl₂(μ‐Y)₂(AsR₃)₂] (Y = OAc or SPh), [MCl(S₂CNEt₂)(AsR₃)] and [PdCp(Cl)(AsiPr₃)] (M = Pd or Pt) have been prepared. All the complexes have been characterised by elemental analyses, IR and ¹H NMR spectroscopy. The stereochemistry of the complexes has been deduced from the spectroscopic data. The structures of [Pd₂Me₂(μ‐X)₂(AsiPr₃)₂] (X = Cl or Pz) have been established by single crystal X‐ray diffraction analyses. Both of the complexes have sym‐trans configuration. Strong trans influence of the methyl group is reflected on the Pd—X bond distances.     

Halogen bonding between substituted chlorobenzene and trimethylamine: Decisive role of σ–hole and C?Cl bond breaking energy

Theoretical studies have been carried out on the halogen bonding interaction between para substituted chlorobenzene (Y C₆H₄Cl, Y = H, NH₂, CH₃, F, CN, NO₂) and N(CH₃)₃ using ab initio MP2/aug‐cc‐pVDZ and DFT based wB97XD/6‐311++G(d,p) methods. The positive electrostatic potential (V_S,max) on the Cl atom and the heterolytic bond breaking enthalpy of the C Cl bond have been calculated and their role on halogen bonding is discussed. The heterolytic bond breaking enthalpy of the C Cl bond is proposed as a measure of the strength of the σ‐hole on Cl atom. The binding strength of the complexes ranging between −6.13 kJ mol⁻¹ and −9.29 kJ mol⁻¹ are linearly related to the V_S,max of the Cl atom and the bond breaking enthalpy of the C Cl bond. In addition, energy decomposition analysis was performed on the halogen bonded complexes via symmetry adapted perturbation theory (SAPT) to predict the dominant energy component and the nature of the N···Cl interaction.     

Monitoring of the synthesis ofcis andtrans ruthenium macrocyclic complexes by reversed-phase high-performance liquid chromatography

Summary The synthesis of the complex [Ru(cyclam)Cl₂]Cl (cyclam=1,4,8,11-tetraazacyclotetradecane) has been monitored by reversed-phase high-performance liquid chromatography. The analytical results obtained during the reaction have shown that it is feasible to identify and isolate the two isomerscis- andtrans- [Ru(cyclam)-Cl₂]Cl. The use of an octadecylsiloxy preparative column enabled the separation and purification of these two isomers and the compounds have been obtained in high purity. The use of reversed-phase high-performance liquid chromatography has afforded complete analytical control of the syntheses of saturated nitrogendonor macrocyclic complexes of ruthenium, enabling identification of thecis andtrans isomers of the complex [Ru(cyclam)Cl₂]Cl.     

Synthesis of new water soluble diorganotin(IV) complexes with hydrazones derived from Girard-T reagent as antibacterial and anticancer agents

Three new water-soluble organotin complexes R₂Sn(5-BrSalGT)Cl [R = Ph, Me] and Ph₂Sn(2-OHNaphGT)Cl have been synthesized by the reaction of R₂SnCl₂ (R = Ph or Me) with Schiff bases derived from condensation of Girard-T reagent with 5-bromosalicylaldehyde and 2-naphthaldehyde, (5-BrH₂SalGT)Cl (1) and (2-OHH₂NaphGT)Cl (2). The synthesized compounds have been investigated by elemental analysis, conductometric measurements, IR, ¹H NMR, and ¹¹⁹Sn NMR spectroscopy. These data show that the deporotonated ligand is coordinated to Sn(IV) via ONO atoms and six-coordinate zwitterionic complexes are formed. The ligands and their complexes were investigated for their in vitro toxicity against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. The results show remarkable antibacterial activity against the studied bacteria. All complexes exhibit more inhibitory effects than the parent ligand. The anticancer activity of all compounds were also performed on HN5 cell line and (2-OHH₂NaphGT)Cl with concentration of 1 mg mL^?1 was found to show higher anticancer activity than other compounds.     

Preparation and photochemistry of macromolecular bound ruthenium(II) complexes in aqueous solutions

Ruthenium(II) polypyridyl complexes with macromolecular ligands poly(methylolacrylamide-co-vinylpyridine) and poly (acrylamide-co-vinylpyridine) have been synthesized. The macromolecular ruthenium (II) complexes which are soluble in water have been characterized and their absorption and emission properties have been studied in aqueous solution. Photolysis of the complex in aqueous solution leads to photoaquation reactions with release of coordinated pyridines of the polymer. In the case of monomeric complex, cis-[Ru(bpy)₂(py)₂]Cl₂, photolysis in water in presence of Cl^? ions produces only the substitution of the pyridine by water whereas in the polymeric complexes, [Ru(bpy)₂(MAAM-co-VP)₂]Cl₂ photolysis in the presence of chloride produces [Ru(bpy)₂(MAAM-co-VP)Cl]Cl and [Ru(bpy)₂(AM-co-VP)Cl]Cl, respectively. Quantum yields for the photosubstitution reactions have been determined and mechanistic details are outlined.     

Austausch von Chlorisotopen am Phosphoratom, 1. Mitt.: Dialkylchlorthiophosphate

Zusammenfassung An den Modellverbindungen Dialkylchlorthiophosphat (RO)₂P(S)Cl (R=Me, Et, n-Pr) und Diphenylchlorthiophosphat (PhO)₂P(S)Cl wurde der Austausch Chlorid—Radiochlorid am Thiophosphorylzentrum untersucht. Die bimolekularen Geschwindigkeitskonstanten, die Aktivierungsenergien und Aktivierungsentropien wurden berechnet. Der Einfluß von Substituenten auf bimolekulare Substitutionsreaktionen am vierfach koordinierten Phosphoratom wurde diskutiert.

---

Chlorine isotopic exchange at phosphorus atoms, I.: Chloridothiophosphates

The chloride—radiochloride ion exchange at the thiophosphoryl centre has been studied using dialkylchloridothiophosphates (RO)₂P(S)Cl (R=Me, Et, n-Pr) and diphenylphosphorochloridothionate, (PhO)₂P(S)Cl, as model compounds. The bimolecular rate constants, energies and entropies of activation have been calculated. Effects of the substituents in the bimolecular displacement reaction on four-coordinated phosphorus atom have been discussed.

---

---

Mit 3 Abbildungen     

Quantum Chemical Calculation of Conformations and Rotation Barriers of Functional Groups in Arylsulfonyl Halides

The semiempirical PM3 method is used to calculate the potential functions of internal rotation of the functional groups –SO₂Cl, –NO₂, –CH₃, –OCH₃, and –NH₂ of benzenesulfonyl halide molecules (PhSO₂Hal, Hal = F, Cl, Br, I) and twelve substituted derivatives of benzenesulfonyl chloride. Molecular conformations have been determined and internal rotation barriers of the functional groups have been calculated. For meta- and para-substituted benzenesulfonyl chlorides, the projection of the S–Hal bond is perpendicular to the plane of the benzene ring. The rotation barriers of the –SO₂Hal group of benzenesulfonyl halides increase in the series Hal = F, Cl, Br, I. The rotation barriers of the –SO₂Cl group of benzenesulfonyl chloride with meta- and para-substituents slightly increase with the electron-donor properties of the substituent. The rotation barriers of the functional groups of ortho-substituted benzenesulfonyl chlorides are 3 or 4 times as high as those of the meta- and para-isomers. For para-substituted benzenesulfonyl chlorides, the rotation barriers of the functional groups increase in the order –CH₃, –NO₂, –SO₂Cl, –OCH₃, –NH₂.     

Kinetics of the reactions of chlorine atoms with CH3ONO and CH3ONO2

The kinetics of the reactions of Cl atoms with CH₃ONO and CH₃ONO₂ have been studied using relative rate techniques. In 700 Torr of nitrogen diluent at 295 ± 2K, k(Cl + CH₃ONO) = (2.1 ± 0.2) × 10⁻¹² and k(Cl + CH₃ONO₂) = (2.4 ± 0.2) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹. The result for k(Cl + CH₃ONO₂) is in good agreement with the literature data. The result for k(Cl + CH₃ONO) is a factor of 4.5 lower than that reported previously. It seems likely that in the previous study most of the loss of CH₃ONO which was attributed to reaction with Cl atoms was actually caused by photolysis leading to an overestimate of k(Cl + CH₃ONO). © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 357–359, 1999     

Monitoring of the synthesis ofcis andtrans ruthenium macrocyclic complexes by reversed-phase high-performance liquid chromatography

Summary The synthesis of the complex [Ru(cyclam)Cl₂]Cl (cyclam=1,4,8,11-tetraazacyclotetradecane) has been monitored by reversed-phase high-performance liquid chromatography. The analytical results obtained during the reaction have shown that it is feasible to identify and isolate the two isomerscis- andtrans- [Ru(cyclam)Cl₂]Cl. The use of an octadecylsiloxy preparative column enabled the separation and purification of these two isomers and the compounds have been obtained in high purity. The use of reversed-phase high-performance liquid chromatography has afforded complete analytical control of the syntheses of saturated nitrogendonor macrocyclic complexes of ruthenium, enabling identification of thecis andtrans isomers of the complex [Ru(cyclam)Cl₂]Cl.     

Platinum(II) and palladium(II) chlorides complexes with purine,pyrimidine,N-ethylimidazole andN-propylimidazole

Summary Platinum(II) and palladium(II) chloride complexes with purine, pyrimidine (pyrimid),N-ethylimidazole(N-EtIm) andN-propylimidazole(N-PropIm) ligands have been prepared and characterized by analysis and spectroscopic methods. The compounds have general formula M(L₁)(L₂)Cl₂ where M=Pt^II, Pd^II; L₁=purine or pyrimid, L₂=N-EtIm orN-PropIm, except the complexes Pt(purine)(pyrimid)Cl₂ and [Pd(purine)(pyrimid)₂Cl]Cl and [Pt(purine)₂ (N-propIm)Cl]Cl·2H₂O.     

Five‐coordinate dinuclar cobalt (II), copper (II), zinc (II) and cadmium (II) complexes with 4‐bromo‐N‐(2‐pyridinylmethylene)benzenamine: Synthesis,characterisation and methyl methacrylate polymerization

A series of late transition metal complexes, [(bpma)Co(μ – Cl)Cl] ₂ , [(bpma)Cu(μ – Cl)Cl] ₂ , [(bpma)Zn(μ – Cl)Cl] ₂ and [(bpma)Cd(μ – Br)Br] ₂ (where bpma is 4‐bromo‐N‐((pyridin‐2‐yl)methylene)benzenamine) have been synthesized and structurally characterized. The X‐ray structures of dimeric complexes [(bpma)M(μ – X)X] ₂ (M = Co, Cu and Zn, X = Cl; M = Cd, X = Br) showed a distorted 5‐coordinate trigonal bipyramidal geometry involving two nitrogen atoms of N,N‐bidentate ligand, two bridged and one terminal halogen atoms. The complex [(bpma)Cu(μ – Cl)Cl] ₂ revealed the highest catalytic activity for the polymerisation of methyl methacrylate in the presence of modified methylaluminoxane with an activity of 9.14 × 10⁴ g PMMA/mol·Cu·h at 60 °C and afforded syndiotactic poly (methylmethacrylate) (rr = 0.69).     

Kinetic study of the reaction of chlorine atoms with CF3I and the reactions of CF3 radicals with O2, Cl2 and NO at 296 K

The kinetics of the gas-phase reaction of Cl atoms with CF₃I have been studied relative to the reaction of Cl atoms with CH₄ over the temperature range 271–363 K. Using k(Cl + CH₄) = 9.6 × 10^?12 exp(?2680/RT) cm³ molecule^?1 s^?1, we derive k(Cl + CF₃I) = 6.25 × 10^?11 exp(?2970/RT) in which E_a has units of cal mol^?1. CF₃ radicals are produced from the reaction of Cl with CF₃I in a yield which was indistinguishable from 100%. Other relative rate constant ratios measured at 296 K during these experiments were k(Cl + C₂F₅I)/k(Cl + CF₃I) = 11.0 ± 0.6 and k(Cl + C₂F₅I)/k(Cl + C₂H₅Cl) = 0.49 ± 0.02. The reaction of CF₃ radicals with Cl₂ was studied relative to that with O₂ at pressures from 4 to 700 torr of N₂ diluent. By using the published absolute rate constants for k(CF₃ + O₂) at 1–10 torr to calibrate the pressure dependence of these relative rate constants, values of the low- and high-pressure limiting rate constants have been determined at 296 K using a Troe expression: k₀(CF₃ + O₂) = (4.8 ± 1.2) × 10^?29 cm⁶ molecule^?2 s^?1; k_∞(CF₃ + O₂) = (3.95 ± 0.25) × 10^?12 cm³ molecule^?1 s^?1; F_c = 0.46. The value of the rate constant k(CF₃ + Cl₂) was determined to be (3.5 ± 0.4) × 10^?14 cm³ molecule^?1 s^?1 at 296 K. The reaction of Cl atoms with CF₃I is a convenient way to prepare CF₃ radicals for laboratory study. © 1995 John Wiley & Sons, Inc.     

Ruthenium(II) 2,2′-bipyridine complexes incorporating substituted phenylazo-(2-(phenylthio))phenylmethine ancillary ligands. Synthesis,crystal structure,spectroscopic and redox properties

Abstract  

Five ruthenium complexes bearing phenylazo-(2-(phenylthio))phenylmethine ligands of the general type trans-[Ru^II(bpy)(L)(Cl)₂] (C1–C5) {L = YC₆H₄N=NC(COCH₃)=NC₆H₄(2-SC₆H₅), H (L1), Cl (L2), OCH₃ (L3), Br (L4), or NO₂ (L5)} have been synthesized. The crystal structure of trans-[Ru(bpy)(L1)(Cl)₂] (C1) is reported and shows no direct metal–S interaction. The complexes have been characterized through spectroscopic (IR, UV/vis and NMR) and electrochemical (CV) techniques. The electrochemical parameters (E _L(L)) of the azoimine ligands are reported.     

3‐Rhoda‐1,2‐diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From CN Functionalization of Ethylene

Rh‐containing metallacycles, [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NR)₂‐]Cl; TPA=N,N,N,N‐tris(2‐pyridylmethyl)amine have been accessed through treatment of the Rh^I ethylene complex, [(TPA)Rh(η²‐CH₂CH₂)]Cl ([ 1 ]Cl) with substituted diazenes. We show this methodology to be tolerant of electron‐deficient azo compounds including azo diesters (RCO₂N?NCO₂R; R=Et [ 3 ]Cl, R=iPr [ 4 ]Cl, R=tBu [ 5 ]Cl, and R=Bn [ 6 ]Cl) and a cyclic azo diamide: 4‐phenyl‐1,2,4‐triazole‐3,5‐dione (PTAD), [ 7 ]Cl. The latter complex features two ortho‐fused ring systems and constitutes the first 3‐rhoda‐1,2‐diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N–N coordination followed by insertion of ethylene into a [Rh]?N bond. In terms of reactivity, [ 3 ]Cl and [ 4 ]Cl successfully undergo ring‐opening using p‐toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh^III(Cl)(κ¹‐(C)‐CH₂CH₂(NCO₂R)(NHCO₂R)]OTs; [ 13 ]OTs and [ 14 ]OTs. Deprotection of [ 5 ]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end‐on coordinated diazene [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NH)₂‐]⁺ [ 16 ]Cl, a hitherto unreported motif. Treatment of [ 16 ]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh^III(κ²‐(C,N)‐CH₂CH₂(NAc)₂‐]⁺, [ 17 ]Cl. Treatment of [ 1 ]Cl with AcN?NAc did not give the Rh?N insertion product, but instead the N,O‐chelated complex [(TPA)Rh^I ( κ²‐(O,N)‐CH₃(CO)(NH)(N?C(CH₃)(OCH?CH₂))]Cl [ 23 ]Cl, presumably through insertion of ethylene into a [Rh]?O bond.     

Thermodynamic Properties of Quaternary Aqueous Solutions of Chlorides Charge-type 1-1*1-1*2-1: NH4Cl + NaCl + YCl2 + H2O with Y ≡ Mg2+, Ca2+, and Ba2+

Thermodynamic properties of quaternary aqueous solutions of mixed chlorides of 1-1*1-1*2-1 charge type with the cations (Na⁺, NH₄ ⁺; Mg²⁺, Ca²⁺, Ba²⁺) were determined using the hygrometric method. The quaternary systems NH₄Cl + NaCl + MgCl₂ + H₂O, NH₄Cl + NaCl + CaCl₂+ H₂O, and NH₄Cl + NaCl + BaCl₂ + H₂O have been studied at 25 °C. The water activities were measured at total molalities from 0.44 mol⋅kg⁻¹ to saturation for different ionic-strength fractions y of NH₄Cl, y=(0.20,0.50,0.80), and different ionic strength ratios z for other solutes, z=(0.20,0.50 and 0.80) for each value of y. The obtained data allows the calculation of osmotic coefficients.     

Transition metal complexes of heterocyclic Schiff base

Metal complexes of Schiff base derived from 2-furancarboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, ¹H NMR, UV-Vis, solid reflectance, magnetic moment, molar conductance and thermal analysis. The ligand dissociation as well as the metal-ligand stability constants have been calculated pH-metrically at 25°C and ionic strength μ=0.1 (1 M NaCl). The complexes are found to have the formulae [M(HL)₂](X)_n·yH₂O (where M=Fe(III) (X=Cl, n=3, y=4), Co(II) (X=Cl, n=y=2), Ni(II) (X=Cl, n=y=2), Cu(II) (X=Cl, n=y=2) and Zn(II) (X=AcO, n=y=2)) and [UO₂(L)₂]·2H₂O. The thermal behaviour of these chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The ligand and its metal complexes show a biological activity against some bacterial species.     

Experimental and computational studies on a new mixed ligand oxido–rhenium(V) compound

A mixed ligand oxido–rhenium(V) complex, [ReOS₃(HL)]Cl.H₂O ( 1p Cl.H₂O), with 3‐thiopentane‐1,5‐dithiolato (S₃) as a tridentate ligand and imidazolidinethione (HL) as an ancillary monodentate sulfur donor co‐ligand, has been synthesized. 1p Cl.H₂O has been characterized by spectral analyses. The X‐ray crystal structure of 1p Cl.H₂O shows that the complex contains a distorted square‐pyramidal “ReOS₄” core. The structural parameters agree with our optimized structure of 1p ⁺. Subsequently, the optimized structure was used to calculate systematically the relative stabilities of a sequence of oxido–Re(V) and the analogous oxido–Tc(V) complexes just by varying the donor sites (N, S, and O) on the tridentate ligand moiety in 1p ⁺. Electrochemical studies on 1p Cl.H₂O show an oxidative rhenium(VI)/ rhenium(V) couple at 1.561 V versus Ag/AgCl under controlled linear diffusion situation. Vibrational frequencies, electronic structures, and redox potential of 1p ⁺ have been calculated theoretically employing density functional theory (DFT) or time‐dependent‐DFT methods. The experimental findings are in excellent agreement with the computed results. The calculated redox potentials of the investigated oxido–Re(V) complexes and their oxido–Tc(V) counterparts are shown to correlate linearly with their respective chemical potential values.