The photolytic reactions of iron thiocarbonato complexes CpFe(CO)2SC(Y)Y′R [Y=Y′=O; R=2-C6H4Cl (1), 4-C6H4Cl (2); Y=S, Y′=O; R=C6H4F (3), Y=Y′=S; R=Ph (4)] with EPh3 (E=P, As, Sb) are performed. Monosubstituted complexes of the general formula CpFe(CO)(EPh3)SC(Y)Y′R [Y=Y′=O; R=2-C6H4Cl (5), 4-C6H4Cl (6); Y=S, Y′=O; R=C6H4F (7), Y=Y′=S; R=Ph (8); E=P (a), As (b), Sb (c)] have been isolated and characterized by spectroscopic analysis (UV–Vis, IR, 1H, 31P NMR) and elemental analysis. The molecular structures of CpFe(CO)(PPh3)SCO2-2-C6H4Cl (5a) and its dicarbonyl parent CpFe(CO)2SCO2-2-C6H4Cl (1) have been determined by single crystal X-ray crystallographic studies.
Extreme events of atmospheric phenomena are often non deterministic in nature, and this has been a major constraint in achieving agricultural sustainability in most developing countries.To facilitate this study, 29 years information of the observed relative humidity of Ogun basin was obtained from the Federal Ministry of Water Resources, Abeokuta, Nigeria. The data collected covers the periods between 1982 and 2009 and were pre-whitened and aggregated into monthly and annual time series. The stationarity of the time series data was achieved through Mann-Kendal non parametric test and spectral analysis. The Mann-Kendal Z-value obtained is -1.37, which gives no reason to expect the presence of trend in the time series. The spectral density plot showed high variance to lower frequency, and this signifies a positive correlation. No evidence of seasonal effect in the series as clearly depicted by the monthly Periodogram. The autoregressive AR-model, moving average MA-model and autoregressive moving average ARMA-models were fitted for the parameter, with the aid of Akaike Information Criterion (AIC), and error terms of FE, MAE, MSE and MAPE. ARMA model of order (2, 2) was found to be the most parsimonious for predicting relative humidity. Results are highly accurate and promising for all models based on Lewis’ criteria. Prediction scheme applied in this research could be considered in situations where database is a problem during model development. Keywords: ARMA model, Autocorrelation, Forecasting,Prediction andRelative humidity
This study was conducted on sachet water samples mostly consumed in Minna Nigeria. Six types of sachet water samples were collected (A, B, C, D, E and F) and the six were randomly selected from the numerous sachet water factory in Minna. The purpose of this study was to determine the quality of sachet water used as drinking water and domestic purpose by looking into the microbiological aspect and several physicochemical analyses such as turbidity, pH and total suspended solid (TSS). The microbiological analyses were performed to trace the presence of indicator organisms and pathogens such as Escherichia coli and total coliform count. However, the total coliforms and E. coli were detected to range between 0 and 43 cfu/100mL while the E. coli ranged between 0.00 and 7.00 cfu/100mL. The pH value was slightly alkaline (pH >6.5) but below 9.5 which within the recommended standards. The TSS for the samples ranged between 45 and 190 mg/L which were very low compared with the recommended values and the turbidity for all the samples were recorded below 2 Nephelometric Turbidity Units (NTU) thus, complying with the regulations. All the water samples were fit to be consumed except those with high values of E. coli and total coliform count. Keywords: Drinking water, filters, microbiology, physicochemical, quality, sachet water
Treatment of the iron selenide (mu-Se)[CpFe(CO)2]2 with one equivalent of 1, 3, 5-C6H3(COCl)3 gave the organoiron selenocarboxylate complex CpFe(CO)2SeCO-3, 5-C6H3(COCl)2 (1), which contains two free acid chloride groups. Complex 1 reacted with amines, thiols, and phenols to produce the corresponding amides CpFe(CO)2SeCO-3, 5-C6H3(CONR2)2 (2), thioesters CpFe(CO)2SeCO-3, 5-C6H3(COSR)2(3), and aromatic esters CpFe(CO)2SeCO-3, 5-C6H3(CO2Ar)2 (4), respectively. Complex 1 was converted into the diacid CpFe(CO)2SeCO-3, 5-C6H3(COOH)2 (5) or the diamide CpFe(CO)2SeCO-3, 5-C6H3(CONH2)2 (6) complexes by reactions with NaOH or NaNH2, respectively. The bis(seleno)-1, 3-(CpFe(CO)2SeCO)2-5-C6H3(COCl) (7) and tris(seleno)-carboxylate 1, 3, 5-(CpFe(CO)2SeCO)3C6H3 (8) complexes were also prepared by controlled reaction of 1, 3, 5-C6H3(COCl)3 with the iron selenide (mu-Se)[CpFe(CO)2]2. Complexes 18 were characterized by spectroscopic techniques (IR, 1H-NMR) and by elemental analysis as well. The X-ray structures of CpFe(CO)2SeCO-3, 5-C6H3(COCl)2 (1) and CpFe(CO)2SeCO-3, 5-C6H3(COSCH2Ph)2 (3b) were determined.
Two newly bifunctional organoiron seleno-terephthalate derivatives (S1 and S2) were synthesized as potential anticarcinogenic compounds. In a previous study, they were found to have antibacterial and/or antifungal activity, while they did not show any mutagenic action. Such compounds were investigated in the present study for their antimutagenic activity. Sodium azide, hydrogen peroxide, and 4-nitro-o-phenylenediamine, as known mutagens for strains TA100, TA102, and TA98 of Salmonella typhimurium, respectively, were used. Both (S1 and S2) compounds showed a strong antimutagenic action of >98% against sodium azide, >70% against hydrogen peroxide, and >65% activity against 4-nitro-o-phenylenediamine. Bearing in mind the strong correlation between mutagenicity and carcinogenicity, the above compounds can be considered as potentially promising anticarcinogens. Therefore, the present results are very encouraging to investigate the above compounds for other biological activities, including their evaluation as anticarcinogens. A suggested mechanism for the antimutagenicity of the tested compounds is presented.
A controlled substitution reaction of the chlorine atoms of 1,3,5-benzenetricarbonyl trichloride by the organoiron fragment (CpFe(CO) 2 S) has been achieved. The complexes CpFe(CO) 2 SCO-3,5-C 6 H 3 (COCl) 2 ( 1 ), 1,3-[CpFe(CO) 2 SCO] 2 -5-C 6 H 3 COCl ( 2 ) and 1,3,5-[CpFe(CO) 2 SCO] 3 C 6 H 3 ( 3 ) were prepared from the reaction of (μ-S x )[CpFe(CO) 2 ] 2 ( x = 3, 4) with 1,3,5-C 6 H 3 (COCl) 3 in a 1:1, 2:1, or 3:1 metal to ligand molar ratio. The reactions of ( 1 ) with amines, thiols, and carboxylic acids produce the trifunctional mono-iron complexes CpFe(CO) 2 SCO-3,5-C 6 H 3 (COY) 2 [Y = NR 2 ( 4 ), SR ( 5 ), OCOR ( 4 )]. The X-ray structure determination of ( 1 ) is reported.
The iron chalcogenides complexes (mu-E-x)[CpFe(CO)(2)](2) (E= S; x= 2-4, E= Se; x= 1) served as excellent precursors for sulfur-or selenium-containing iron complexes. They are reactive toward acid chlorides, sulfonyl chlorides, chloroformates, chlorothioformates, chlorodithioformates, and O-alkyloxalyl chlorides. These reactions produced complexes of the general formula CpFe(CO)(2)EZ (E= S, Se; Z= COR, SO2R, CO2R, C(S) OR, CS2R, COCO2R). Treatment of these chalcogenides with terephthaloyl chloride gave either [CpFe(CO)(2)ECO](2)(4-C6H4) or CpFe(CO)(2)ECO-4-C6H4COCl, depending on the molar ratio of the reactants. The latter complexes react with amines, phenols, carboxylic acids and thiols to give the bi-functional products CpFe(CO)(2)ECO-4-C6H4COY (Y= NR2, OAr, OCOR, SR).The reactions of CpFe(CO)(2)ECOR with APh(3) (A= P, As, Sb) gave exclusively the monosubstituted products CpFe(CO)(APh(3)) ECOR. However the corresponding reactions with bis(phosphine) ((PP)-P-boolean AND) ligands produce the monosubstituted CpFe(CO)(kappa(1), P-(PP)-P-boolean AND) SCOR and/or the disubstituted CpFe(kappa P-2, P-(PP)-P-boolean AND) SCOR complexes.
The reaction of 1-substituted benzyl-1H-1,2,3-triazole-4-carbohydrazides 2a-h with equimolar amounts of isothiocynate produces 1-(1-substituted benzyl-1H-1,2,3-triazole-4-arbonyl)-N-phenylhydrazinecarbothioamide 3a-h. Treatment of 3a-h with sodium hydroxide afforded 5-(1- substituted benzyl-1H-1,2,3-triazol-4-yl)-4-phenyl-4H-1,2,4-triazole-3-thiol 4a-h. Nucleophlic addition of the corresponding sodium salts of 4a-h to alkyl halide (methyl iodide or benzyl bromide) affords the 1-substituted benzyl-4-(5-(alkylthio)-4-phenyl-4H-1,2,4-triazol-3-yl)-H-1,2,3-triazole 5a-h and 6a-h.
The organic transformation reactions of CpFe(CO)2SeCO(C6H4)COCl with primary amines, secondary amines, thiols and carboxylic acids in the presence of pyridine afforded the bifunctional complexes CpFe(CO)2SeCO(C6H4)COX (X = RNH, RR'N, RS, RCOO) in fairly good yields. The synthesized complexes were characterized by elemental analyses, IR and 1 H NMR spectra.
In this publication we report some of our work in which bis-triazoles 3a-u and monotriazoles 5a-u and 7a-c were prepared via 1,3-dipolar cycloaddition reaction of azide derivatives 1a-u and 6a-c with benzoquinone 2 and naphthoquinone 4. Products were characterized by 1H-NMR, IR and mass spectroscopy, as well as elemental analysis.
Photolytic substitutions of iron selenocarboxylate complexes CpFe(CO)2SeCOR with triphenylphosphine, triphenylarsine or triphenylantimony (EPh3) gave exclusively the monosubstituted complexes CpFe(CO)(EPh3)SeCOR [R = 3,5-C6H3(NO2)2(1), 4-C6H4NO2(2), Ph (3), 2-C6H4Me (4), and E = P (a), As (b), Sb (c)] in high yields.
Controlled photolytic CO-substitution reaction of the organoiron thiocarboxylate complexes CpFe(CO)2SCOR (R=CH3, 2-NO2C6H4, 4-NO2C6H4, 3,5-(NO2)2C6H3) with diphosphines (Ph2P(CH2)nPPh2) [n=1 (dppm), n=2 (dppe)] at 0 °C using 1:1 (metal:ligand) molar ratio afforded exclusively the monosubstituted complexes CpFe(CO)(Ph2P(CH2)nPPh2)SCOR. The complex CpFe(CO)(Ph2PCH2P=S(Ph)2)SCO-3,5-(NO2)2C6H3 has been prepared and its X-ray structure was determined.
The photolytic CO-substitution reaction of the organoiron thiocarboxylate complexes CpFe(CO)2SCOR (R=CH3, 2-CH3C6H4, 2-NO2C6H4, 4-NO2C6H4, 3,5-(NO2)2C6H3) with diphosphines (Ph2P(CH2)nPPh2) [n=1 (dppm), n=2 (dppe), n=3 (dpppr), n=4 (dppb), n=5 (dppp), n=6 (dpph)] at room temperature using 1:2 (metal–ligand) molar ratio afforded exclusively the disubstituted complexes CpFe(Ph2P(CH2)nPPh2)SCOR when n=1, 2 and 3 and the monosubstituted analogs CpFe(CO)(Ph2P(CH2)nPPh2)SCOR when n=4, 5 and 6. This reaction was found to be strongly influenced by the backbone length of the diphosphine ligand, the nature of the R group of the thiocarboxylate moiety and the metal–ligand molar ratios. The crystal structure of CpFe(dppm)SCO(3,5-(NO2)2C6H3) was determined.
A new series of bifunctional organoiron thio- and seleno-terephthalate complexes - (eta-C5H5)Fe(CO)(2)ECO(C6H4)COX [E = S; X = C6H11NH, (C2H5)(2)N; and E = Se; X = P - CH3 - C6H4 - NH, C6H5 - C2N2O - S, m - NO2 - C6H4-CH = CH - COO] - has been synthesized via the organic transformation reactions of the terephthaloyl chloride precursors eta-(C5H5)Fe(CO)(2)ECO(C6H4)COCl with the desired nucleophiles. These new complexes were characterized by elemental analysis, IR and H-1 NMR spectra. The above complexes, in addition to some other selected analogues, were tested for their antifungal, antibacterial and mutagenic activity. Our results show that all the selenium-containing compounds have antifungal activity on Candida albicans and antibacterial effects against Bacillus subtilis and Staphylococcus aureus. Four of the six selenium-containing derivatives exhibited growth inhibitory effects against Pseudomonas aeruginosa and/or Escherichia coli. Sulfur-containing derivatives elicited activity against C albicans, and each one of them showed activity against at least one of the bacterial strains that have been used in this investigation. Two selenium-and two sulfur-containing derivatives showed mutagenic activity against one or more than one strain of the Salmonella typhimurium using the Ames test. Copyright (C) 2001 John Wiley Sons, Ltd.
Organoiron thio- and seleno-terephthaloyl chloride complexes CpFe(CO) 2 ECO(C 6 H 4 )COCl (E = S and Se) react with NaOH and NaNH 2 to give quantitative yields of the acid Cp(CO) 2 ECO(C 6 H 4 )CO 2 H and the amide CpFe(CO) 2 ECO(C 6 H 4 )CONH 2 respectively. These amide and acid derivatives react with the terephthaloyl chloride complexes to give a new series of imide-bridged [CpFe(CO) 2 ECO(C 6 H 4 )CO] 2 NH and anhydride-bridged [CpFe(CO) 2 ECO(C 6 H 4 )CO] 2 O organoiron dinuclear homo and hetero dichalcogeno terephthalate complexes. The complexes were characterized by elemental analysis, i.r. and 1 H-n.m.r. spectra.
A new series of organoiron bifunctional complexes (C5H5)Fe(Co)(2)SCO(C6H4)COX (X = RNH, R2N, RO) has been prepared by the reaction of (C5H5)Fe(CO)(2)SCO(C6H4)COCl with primary amines, secondary amines and phenols respectively. The synthesized complexes have been characterized by elemental analysis, IR and H-1 NMR spectra. The reactivity of the above nucleophiles towards the terephthaloyl chloride complex (C5H5)Fe(CO)(2)SCO(C6H4)COCl is also discussed.
The kinetics of the photolytic CO-substitution of Cp′Fe(CO) 2 SCOR [Cp′ = C 5 H 5 , Bu t C 5 H 4 , 1,3-Bu 2 t C 5 H 3 ; R = Me, Bu t , Ph, 2-(O 2 N)C 6 H 4 , 3-(O 2 N)C 6 H 4 , 4-(O 2 N)C 6 H 4 , 3,5-(O 2 N) 2 C 6 H 3 ] with PPh 3 were studied in CH 2 Cl 2 at 0 °C by i.r. spectroscopy. The reactions yielded exclusively the mono-CO-substituted derivatives, Cp′Fe-(CO)(PPh 3 ) SCOR, and were found to follow second order kinetics with first order dependence on the concentration of each reactant. The differences in rates are discussed in terms of current knowledge pertaining to such reactions. An associative mechanism is proposed to account for the kinetic data of the reactions described.