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1

NMR Studies of Tautomerism and Protonation Patterns in Bis(6-purinyl) Disulfide and Ionic Forms of 6-Mercaptopurine

Pazderski L., Toušek J., Sitkowski J., Kozerski L., Szłyk E

Polish Journal of Chemistry

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2007

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Vol. 81, nr 2

193-210

EN

1H-13C and 1H-15N HMBC-NMR spectroscopy was applied to study tautomerism and the protonation patterns in 6-mercaptopurine (6mpH) derivatives: bis(6-purinyl) disulfide ((6puS)2), 6-mercaptopurinium cation (6mpH2 + ) and purine-6-thiolate anions (6mp–, 6mp-deH2–). 1H, 13C, 15N resonances were assigned and the respective delta 1H, delta 13C, delta 15N chemical shifts as well as JHC, JHN coupling constants determined. Quantum-chemical NMR calculations by GIAO method (B3LYP/6-31G**//RHF/6-31G*) allowed to evaluate the ratio of N(1), N(3), N(7), N(9)H : N(1), N(3), N(7)H, N(9) tautomeric forms for the DMSO-solvated (6puS)2 molecules as ca. 9:1. The existence of “semi-protonated” 6mpHźH3O+ species, intermediate between 6mpH and 6mpH2 + , and readily oxidized to (6puS)2 was suggested in the DMSO-d6 + HCl solution. Further hydrolysis and oxidation of the formed disulfide lead to the derivatives of purine-6-sulfenic and purine-6-sulfinic acid.

2

Multinuclear NMR and MS Characterization of Silver(I) Perfluorocarboxylates Complexes with 1,4-Bis(diphenylphosphino)butane

Szymańska I., Goliński A., Pazderski L., Szłyk E

Polish Journal of Chemistry

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2007

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Vol. 81, nr 3

299-311

EN

Ag(I) perfluorinated carboxylates complexes with 1,4-bis(diphenylphosphino)butane (dppb) of general formulae [Ag2(dppb)(RCOO)2]n, where R = C2F5, C3F7, C4F9, C6F13, C8F17 have been prepared and characterized by MS, 1H, 13C, 19F, 31P NMR and IR spectroscopy. In the solid state Ag(I) compounds are most likely tetranuclear species bridged by both diphosphines and carboxylates, because MS studies revealed multinuclear metallated species with bridging dppb and carboxylates. Variable temperature (VT) 31P NMR spectra demonstrate that studied complexes form binuclear species bonded by diphosphine with intermolecular diphosphine exchange, in chloroform solution. Thermal studies of Ag(I) compounds revealed three stages decomposition processes (exothermic) resulting in metallic silver formation in the range 713-853 K.

3

Determination of tetracyclines by near-infrared (NIR) spectroscopy and partial least-squares (PLS) regerssion method

Szłyk E., Kowalczyk-Marzec A., Koter I.

Chemia Analityczna

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2007

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Vol. 52, No. 4

605-617

EN

Oxytetracycline hydrochloride (OTC), tetracycline hydrochloride (TC), and chlortetracyc-line hydrochloride (CTC) were determined in aqueous solutions by NIR spectroscopy and partial least-squares (PLS) regression. For absorption bands selected from the range 6200-5500 cm"1, chemometric models were elaborated applying principal component analysis (PCA). Thirty aqueous calibration solutions of tetracyclines covering the concentration range of 1.0-6.1 mg mL-1 were prepared. For quantitative analysis of the anaiytes, NIR-PLS models were used. Detection limits (DL) of OTC, TC, and CTC were 0.20, 0.25, 0.29 mgmL-1 , and quantification limits (QL) were 0.61, 0.74, 0.87 mgmL-1 , respectively. The estimated purities of OTC, TC. and CTC were compared to these obtained by the reference HPLC method. No statistically significant differences between the results obtained in both methods were found. According to the regulations in Pharmacopoeias (USP, EP, BP), the devel

PL

Oznaczono chlorowodorek oksytetracykliny (OTC), chlorowodorek, telracykliny (TC) i chlorowodorek chlorotetracykliny (CTC) w środowisku wodnym z wykorzystaniem spektroskopii NIR i metody cząstkowych najmniejszych kwadratów (PLS). Model kalibracyjny PLS został przygotowany dla 4 pasm absorpcyjnych z zakresu 6200-5500 cm-1. Do kalibracji użytoroztworów tetracyklin (Sigma, n =30, zakres: 1,0-6,1 mg mL-1), dla których opracowano model PLS analizy wodnych roztworów OTC, TC i CTC (Biowet. Pl), uzyskując granicę wykrywalności (DL): 0,20, 0,25, 0,29 mg mL-1 i granicę oznaczalności (QL): 0,61, 0,74, 0,87 mg mL-1 odpowiednio dla OTC, TC i CTC. Otrzymane wartości czystości związków, porównano do wartości otrzymanych \v metodzie odniesienia (I IPLC) uzyskując parametry statystyczne analizy OTC, TC i CTC wymagane dla procedur farmakopealnych.

4

Determination of tetracycline hydrochloride by NIR spectroscopy

Szłyk E., Kowalczyk-Marzec A., Szydłowska-Czerniak A.

Chemia Analityczna

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2007

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Vol. 52, No. 2

281-293

EN

Tetracycline hydrochloride (TC) has been determined in the aqueous solution and in the solid phase by NIR spectroscopy. Principal Component Analysis (PCA) and Partial Least-Squares Calibration procedures have been applied to the set of 30 calibration solutions of TC and laboratory-made pastilles (400 mg-in-weight each). PLS simulation models have been constructed based on the absorbance measurements in the range 4000-10000 cm-1. For calibration, the following analytical bands have been used: 5936, 5694, 4849. 4440. 4147cm-1 for the solid form, and 7135, 5933,5253,4922,4426,4136cm-1 for aqueous solutions. 2.0-11.0 mg mL-1working solutions of tetracycline and laboratory pastilles containing 10-110 mg of TC (2.5-25.0%) were used for calibration. Quantification limit (QL) and detection limit (DL) for TC were, respectively: 2.12% and 1.52% for the solid form, and 0.480 mg mL-1 and 0.266 mg mL-1 for the aqueous solution. Veterinary drug Vetacyclinum Pulvis (VP) was determined in solution and in 20 laboratory-made pastilles (400 mg-in- weight each). The results were compared to these obtained by the reference HPLC method. The proposed NIR method allowed fast determination of TC in the solid phase and in the solution.

PL

Zastosowano spektroskopię w bliskiej podczerwieni (NIR) do oznaczania chlorowodorku tetracykliny (TC) w roztworach wodnych i fazie stałej. W oznaczaniu 30 roztworów wzorcowych TC i pastylek laboratoryjnych, każda o masie 400 mg, wykorzystano metodę głównych składowych (PCA) oraz cząstkowych najmniejszych kwadratów (PLS). W celu zbudowania modelu kalibracyjnego PLS wykorzystano wartości absorbancji następujących pasm analitycznych: 5936, 5694, 4849, 4440, 4147 cm-1 w przypadku TC w pastylkach oraz 7135, 5933, 5253. 4922, 4426, 4136 cm-1 w przypadku wodnych roztworów TC. Kalibracje przeprowadzono dla roztworów standardowych tetracykliny o stężeniu 2,0-11,0 mg mL~' oraz dla pastylek laboratoryjnych zawierających 10-110 mg TC (2,5-25,0%). Obliczone granice oznaczalności (QL) oraz wykrywalności (DL) wynosiły odpowiednio 2.12% i 1,52% dla formy stałej oraz 0,480 mg mL-1>, i 0,266 mg mL-1>, dla roztworów wodnych. Zaproponowaną metodę NIR zastosowano do oznaczenia zawartości TC w preparacie farmaceutycznym Vetacyclinum Pulvis (VP)> przygotowując roztwory wodne badanego leku oraz 20 pastylek preparatu, każda o masie 400 mg. Wyznaczone zawartości substancji czynnej TC w preparacie VP porównano z wynikami uzyskanymi metodą referencyjną (HPLC). Metoda NIR pozwala na szybką analizę ilościową TC w formie stałej oraz w postaci roztworów wodnych.

5

Determination of moisture in veterinary drugs by NIRS method

Szłyk E., Kowalczyk-Marzec A., Szydłowska-Czerniak A.

Chemia Analityczna

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2007

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Vol. 52, No. 2

307-325

EN

The near-infrared spectroscopic (NIRS) method and multiple linear regression (MLR) method have been used for determination of the moisture content in tetracycline hydrochloride and oleandomycine phosphate in powdered forms. Chemometric calibration model has been developed using two absorption bands: at 5170 and 6850 cm-1. The determined mean moisture content in veterinary drugs Vetacyclinum pulvis (VP) and Polzomycine (P) varied in the range 2.52-3.54%. Detection limit and quantification limit were 0.31% and 0.92% for VP, and 0.58% and 1.75% for P, respectively. Intra-day and intermediate precisions of the proposed determination by the NIR method have been evaluated and RSD values of 0.99% and 1.89% for VP, and 0.85% and 1.13% for P were obtained. These numbers indicate reasonable repeatability and intermediate precision of NIR method. The accuracy of this method was compared to that of the reference Karl Fischer's method, and they were found consistent (99.2-100.1% and 99.1-99.8%, respectively), which proves applicability of the proposed NIR method in the routine determination of the moisture content in veterinary drugs.

PL

Spektroskopię w bliskiej podczerwieni (NIRS) oraz metodę regresji wielokrotnej (MLR) zastosowano do oznaczania wilgoci w stałych preparatach farmaceutycznych Vetacyclinum pulvis (VP) i Polzomycynie (P) zawierających chlorowodorek tetracykliny oraz fosforan oleandomycyny jako substancje czynne. Równania regresji dla krzywych kaiifaracyjnych wyznaczono w oparciu o dwa pasma analityczne 5170 i 6850 cm-1. Oznaczona zawartość wilgoci w badanych lekach weterynaryjnych VP i P mieściła się w granicach 2.52-3,54%. Wyznaczone granice wykrywalności i oznaczalności wynosiły odpowiednio 0,31% i 0,92% VP oraz 0,58% i 1,75% P. Oceniono również powtarzalność i precyzję pośrednią proponowanej metody NIR. Wartości RSD (0,99% i 1,89% dla VP oraz 0,85% i 1,13% dla P) świadczą o tym. że proponowana metoda NIR pozwala na uzyskanie wyników powtarzalnych i o precyzji pośredniej zgodnej z zaleceniami fannakopealnymi (FP VI and EPh 2002). Porównywalna dokładność proponowanej metody, wyrażona wartościami odzysku (99,2-100,1%) farmakopealnej metody K. Fischera (99,1-99,8%) świadczy o możliwości zastosowania techniki NIR do rutynowego oznaczania wilgoci w lekach weterynaryjnych.

6

Determination of cholic acid in bile and pharmaceutical preparation

Kurzawa M., Koter I., Szłyk E.

Chemia Analityczna

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2006

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Vol. 51, No. 3

411-418

EN

New analytical procedures for determination of cholic acid in powdered and liquid bile samples and in Tympachol, pharmaceutical preparation derived from bile have been developed. Spectrophotometric methods are based on the reaction between cholic acid and aldehydes (5-methyl furfural, 5-methyl-2-tiophene and ortophtalic) in sulfuric acid solution. Molar absorptivity coefficients for the obtained species ranged from 1.38 x 104 to 6.94 x l04 L mol-1 L mol-1and correlation coefficient exceeded 0.9984. The RSD values for the developed procedures were not higher than 2.85% for the powdered bile sample. 3.31% for the liquid bile sample, and 3.48% for Tympachol. Accuracy and precision were investigated applying the Student-t and F-Snedecor tests and the results were compared to those obtained by Polish Standard and HPLC methods.

PL

W pracy opisano nowe analityczne procedury do oznaczania kwasu cholowego w żółci sproszkowanej, piynnej oraz w Tympacholu - preparacie farmaceutycznym na bazie żółci. Metody spektro foto metryczne zostały oparte na reakcji pomiędzy kwasem cholowym a aldehydami: 5-metylofurfuraIem, 5-metylo-2-liofenowym oraz ortoftalowym w środowisku kwasu siarkowego. Molowe współczynniki absorpcji dla otrzymanych związków wynosiły od 1,38 x 104 do 6,94 x 104 L mol-1 L mol-1, a współczynniki korelacji przekraczały 0,9984. Wartości RSD dla wszystkich opracowanych procedur w przypadku żółci sproszkowanej były niższe niż 2,85%, w przypadku żółci płynnej niższe niż 3,31%, natomiast w przypadku preparatu nie przekraczały 3,48%. Dokładność i precyzję opracowanych metod porównano z wynikami uzyskanymi metodą opisaną w Polskich Normach oraz z wynikami uzyskanymi metodą HPLC, stosując tesly t-Studenta i F-Snedecora.

7

Synthesis and Characterization of Ionic Cu(I) Perfluorocarboxylate Compounds with 1,4-Bis(diphenylphosphino)butane

Szymańska I., Pazderski L., Kucharek R., Szłyk E.

Polish Journal of Chemistry

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2005

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Vol. 79 / nr 11

1705-1711

EN

A series of ionic Cu(I) perfluorocarboxylate compounds with 1,4-bis(diphenyl - phosphino)bu tane (dppb) of gen eral formula [Cu(dppb)2](RCOO), where R = C2F5, C3F7, C4F9, C6F13, C8F17, was prepared and characterized with MS, IR and 1H, 13C, 19F, 31P NMR spectroscopy. The studied species contained monomeric, bis-chelated [Cu(dppb)2]+ cations and uncoordi nated RCOO- anions. The Cu(I) coordi nation of the diphosphines resulted in slight high-frequency shifts of the 31P NMR resonances of the equivalent phosphorus atoms.

8

Multinuclear NMR and Thermal Studies of New Silver(I) Silylated Carboxylates with Triphenylphosphine

Szłyk E., Szymańska I., Szczęsny R.

Polish Journal of Chemistry

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2005

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Vol. 79 / nr 4

627-635

EN

Me3SiCH2COOAg, [Ag(Me3SiCH2COO)(PPh3)] and [Ag(Me3SiCH2CH2COO)(PPh3)] were prepared and characterized in solution by 1H, 13C, 29Si, 31P and 29Si, 31P CPMAS NMR. Spectral analysis suggests bidentate bridging carboxylates and monodentately bonded PPh3 in solution and in the solid state. Two crystallographically inequivalent molecules of PPh3 appeared in the solid state, what is evident from 31P CPMAS NMR. Thermal studies of both complexes demonstrate two stage decomposition process (exothermic followed by endothermic) with formation of metallic silver in the range 483-548 K. TGA/IR and MS studies of Me3SiCH2COOAg and [Ag(Me3SiCH2COO)(PPh3)] revealed volatile products of decomposition (CO2, Me3 Si-) and recombination reactions such as (Me3SiCH2CO)2O, (Me3Si)2O. The mechanism of complexes thermal decomposition is proposed.

9

Chemical Vapour Deposition (CVD) of metallic layers prepared from silver carboxylates complexes with tertiary phosphines

Szczęsny R., Szymańska I., Piszczek P., Dobrzańska L., Szłyk E.

Materials Science Poland

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2005

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Vol. 23, No. 3

671--676

EN

Silver fluorocarboxylate tertiary phosphines complexes [Ag(O2CR)(PR,3)] (where R = CF3, C2F5, Me3SiCH2; R, = Me, Et) have been used as precursors in the hot-wall Chemical Vapour Deposition (CVD) of silver films. Pyrolysis of Ag(I) compounds and thermal stability of metallic species transported in the gas phase were characterized by temperature variable IR (VT-IR) and MS (MS-EI) methods. Metallic films were produced between 403 and 423 K under deposition pressure 0.8 2.0 mbar, under Ar atmosphere, on Si(111) substrates. They were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) integrated with EDX equipment.

10

Conductometric and spectrophotometric determination of haloperidol, droperidol and pimozide

Kurzawa M., Kowalczyk-Marzec A., Szłyk E.

Chemia Analityczna

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2004

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Vol. 49, No. 1

91-99

EN

Spectrophotometric and conductometric determination of haloperidol (HAL), droperidol (DRO) and pimozide (PIM) has been described. Spectrophotometric method is based on the reaction of HAL and PIM with [Cr(NCS)6]3-, [BiI6]3- and picric acid (PA). Calibration plots are consistent with Beer's law in the following concentration ranges: 0.15-1.14 and 0.18-2.68 mg mL-1 for HAL and PIM with [Cr(NCS)6]3-; 0.2101.57 mg mL-1 for HAL with [BiI6]3-, and 0.06-0.91 mg mL-1 and 0.07-0.7 mg mL-1 with PA for HAL and PIM, respectively. Conductometric titrations were performed with (NH4)6Mo7O24, NaVO3 and NaAsO2 as titrants. The proposed methods are accurate and precise with the relative standard deviation less than 1%. One used 2.5-12.5 mg of each pharmaceutic, depending on the titrant applied. The conductometric titrimetry can be successfully applied to the determination of the studied drugs in commercial preparations.

PL

Opisano spektrofotometryczną i konduktometryczną metodę oznaczania haloperidolu (HAL), droperidolu (DRO) i pimozydu (PIM). Metoda spektrofotometryczną jest oparta na reakcji HAL i PIM z jonami kompleksowymi [Cr(NCS)6]3-, [BiI6]3-oraz kwasem pikrynowym (PA). Krzywa kalibracyjna spcinia prawo Beera w następujących zakresach stężeń: 0.18-2.68 mg mL-1odpowiednio dla HAL i PIM z [Cr(NCS)fi;p-; 0,21-1,57 ugmL(-1) dla HAL z [BiI(6), oraz 0,06-0,91 ug mL-1 i 0,07-0,7 ug mL(-1) z PA odpowiednio dla HAL i PIM. Miareczkowanie konduktometryczne wykonano przy użyciu następujących titrantów: (NH4)6Mo7O24, NaVO3 NaAsO2. Proponowane metody charakteryzują się niską wartościąRSD (poniżej 1%), co świadczy o ich precyzji i dokładności. Do oznaczeń używano od 2,5 do 12,5 mg ieku w zależności od użytego titranta. Miareczkowanie konduktometryczne może być z powodzeniem wykorzystane do oznaczania badanych leków w preparatach farmaceutycznych.

11

Copper(I) complexes as potential CVD precursors - studies in the liquid state and gas phase

Szymańska I., Kucharek R., Szłyk E.

Materials Science

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2003

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Vol. 21, No. 2

245-250

EN

Cu(I) complexes with trimethyl phosphite and aliphatic perfluorinated carboxylates of the type [Cu2{P(OMe)3}2(m-RCOO)2] where R = CF3, C2F5, C3F7, C6F13, C7F15, C8F17, C9F19 have been prepared as viscous liquids. In the liquid state the spectroscopic results suggest the dimeric structures for complexes, where the metal ions are linked by the bridging carboxylates. This type of bonding was revealed in the gas phase as well. In the MS conditions the most intensive signals were observed for the [Cu2(RCOO)]+ and [Cu2(RCOO)2]+ fragments. Thermal decomposition of complexes proceeds as a multistage process, yielding a Cu2O in the most of cases.

12

Dimeric Silver(I) Complexes with Trimethylphosphine and Aliphatic Perfluorinated Carboxylates

Szłyk E., Łakomska I.

Polish Journal of Chemistry

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2002

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Vol. 76 / nr 10

1399-1403

EN

Silver(I) complexes with trimethylphosphine and perfluorinated carboxylates of general formula [{Ag(PMe3)2}2(_-OOCR)2], where R = CF3, C2F5, C3F7, C4F9, C7F15, have been prepared and characterized with IR, 1H, 13C, 19F, 31P NMR. Spectral analysis suggests four coordinated Ag(I) with two monodentate trimethylphosphine and bidentate carboxylates forming bridges between silver(I) ions. Thermal decomposition process was studied between 293-973 K in nitrogen. Decomposition proceeds in one exothermic stage corresponding to the elimination of perfluorinated carboxylate and trimethylphosphine. The final product was a mixture of metallic silver and carbon, formed between 473-633 K.

13

Conductometric determination of phenothiazine derivatives by precipitation titration

Kowalczyk-Marzec A., Kurzawa M., Szydłowska-Czerniak A., Szłyk E.

Chemia Analityczna

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2002

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Vol. 47, No. 4

613-618

EN

Results of the conductometric titration of phenothiazine derivatives: trifluoperazine dihydro-chloride (TPE), triflupromazine hydrochloride (TFP) and prochlorperazine dimaleate (PCP) in aqueous and ethanol solutions, with ammonium molybdate(VI), sodium vanadate(V) and sodium arsenate(III) as the titrants, are reported. The method was found to be highly accurate, precise and having relative standard deviation of less then 1% (in 0.5 x 10(-3) to 1.0 x 10(-3) mol L(-1) analyte concentration range). The conductometric titration was applied for the determination of the studied compounds in the presence of NaCl and revealed a good accuracy.

PL

Przedstawiono wyniki miareczkowania konduktometrycznego pochodnych fenotiazyny: dichlorowodorku trifluoperazyny (TPE), chlorowodorku triflupromazyny (TFP) i dimalei-nianu proch lorperazyny (PCP) w wodnym i etanolowym roztworze z molibdenianem(VI) amonu, wanadanem(V) sodu i arsenianem(IIl) sodu jako titrantami. Metoda okazała się bardzo dokładna, precyzyjna, z odchyleniem standardowym mniejszym niż l % (w zakresie stężeń od (in 0,5 x 10(-3) do 1.0 x 10(-3) mol L(-1). W celu oznaczenia badanej substancji zastosowano miareczkowanie konduktometryczne w obecności NaCl, a uzyskane wyniki były zgodne z wynikami dla czystego leku.

14

New Polymeric Copper(II) Complexes with Tributy I Phosphite and Perfluorinated Carboxylates

Szłyk E., Szymańska I., Kucharek R., Wrzeszcz G., Rozpłoch F.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 2

215-222

EN

New Cu(II) complexes with tributyl phosphite and aliphatic perfluorinated carboxylates [Cu{P(OBu)3}(ž-OH)(ž-RCOO)]n, where R = CF3, C2F5, C3F7, C6F13, C7F15, were obtained and their spectroscopic (UV-VIS, EPR, MS, IR) and thermal properties were studied. Mass spectra were in favour of the bridging coordination carboxylates and monodentate phosphite and suggest a polymeric structure. EPR spectra and magnetic susceptibility measurements indicate the formation of pentacoordinated Cu(II) in polymeric complexes. Examination of COO absorption bands suggests bridging carboxylates as well as a hydroxo group, whereas tributyl phosphite is monodentately bonded. Thermal decomposition is a multistage process, which in nitrogen and air yields a mixture of Cu2O and Cu2P2O7.

15

New Optically Active Manganese(II) Complexes with Schiff Bases Obtained from (1R,2R)-(-)-1,2- Cyclohexanediamine and Salicylaldehyde Derivatives

Szłyk E, Surdykowski A., Goździkiewicz M.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 11

1781-1784

16

New Copper(I) Perfluorinated Carboxylates Complexes with Bis(diphenylphosphine)methane

Szłyk E., Kucharek R., Szymańska I.

Polish Journal of Chemistry

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2001

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Vol. 75, nr 3

337-344

EN

Copper(I) perfluorinated carboxylates complexes with bis(diphenylphosphine)methane (dppm) of general formula [Cu2(ž-dppm)3(RCOO)2] dppm, whereR=C2F5, C4F9, C6F13, C8F17, C9F19, have been prepared and characterized by vibrational, 31P CPMASNMRand 13C CPTOSSB NMR mass spectra in the solid state. 1H, 13C, 19F NMR and variable temperature 31P NMR spectra were measured in solution. Temperature variable 31P NMR spectra revealed at least three dimeric species in equilibrium. IR and mass spectra analyses suggest dimeric complexes with three bridging diphosphines and monodentate carboxylates in the solid state.

17

New Polymeric Copper(II) Complexes with Triphenyl Phosphite and Perfluorinated Carboxylates

Szłyk E., Szymańska I., Wrzeszcz G., Rozpłoch F.

Polish Journal of Chemistry

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2000

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Vol. 74, nr 7

909-918

EN

New Cu(II) complexes with triphenyl phosphite and aliphatic perfluorinated carboxylates [Cu{P(OC6H5)3}(u-OH)(u-RCOO)]n (where R=CF3, C2F5, C3F7, C6F13, C7F15, C8F17, C9F19) were obtainedf and their spectroscopic and thermal properties studied. EPR spectra and magnetic susceptibility measurments indicate the formation of polymeric complexes. Examination of COO absorption bands suggests bridging carboxylates as well as a hydro group, whereas triphenyl phosphite is monodentately bonded. Thermal decomposition is a multistage process, which in nitrogen yields a mixture of Cu, Cu2O and Cu2p2O7 but in air - pure u2P2O7.

18

Multinuclear NMR Characterization of Ag(I) Perfluorinated Carboxylates Complexes with Bis(diphenylphosphino)methane

Szłyk E., Goliński A.

Polish Journal of Chemistry

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2000

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Vol. 74, nr 7

895-901

EN

Ag(I) perfluorinated carboxylate complexes with bis(diphenylphosphino0methane (dppm) of general formula [Ag2(RCOO)2(dppm)], where R=CF3, C3F7, C4F9, C6F13, C9F19 were synthetized and spectroscopically (1H,13C,31P,19F, NMR and IR) characterized. Temperature variable 31P NMR spectra were recorded and 1J(107Ag-31P), ysis of coordination shifts and coupling constants are in favour of dimetric trigonal Ag(I) complexes with bridging carboxylates and dppm in solution. IR spectra suggest the same coordination mode in the solid state.

19

Spectroscopic and Thermal Studies of Silver(I) Complexes with Aliphatic Carboxylates and Triphenylphosphine

Szłyk E., Łakomska I., Surdykowski A., Goliński A.

Polish Journal of Chemistry

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1999

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Vol. 73, nr 11

1763-1769

EN

Results of spectral analysis are in favour of Ag(I) trigonal coordination with unidentately bonded triphenylphosphine and bidentate carboxylates, forming bridges between silver(I) ions. Thermal decomposition was studied in 293-973 K range in nitrogen. The multistage decomposition initiates with the detachment of carboxylates and is followed by triphenylphosphine dissociation. The final product is metallic silver, formed between 605-683 K.

20

Studies of Au(I) complexes with perfluorinated carboxylates and trimethylphosphine

Łakomska I., Grodzicki A., Szłyk E.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 3

492-497

EN

Au(I) complexes of the type RCOOAuL, where R=C6F13, C7F15, C8F17, C9F19, C6F5, OOC(C3F6) and L - trimethylphosphine (Me3P) were synthesized and characterized by spectroscopic (IR, (13)C, (19)F, (31)P NMR) and thermal methods. Spectroscopic results favour two coordinated Au(I) with unidentate bonded trimethylphosphine and carboxylates, whereas in the case of hexafluoroglutarate a dimeric structure has been found. The mode of carboxylates binding was proposed basing on the chemical shift of COO group in (13)C NMR spectra and splitting of COO asymmetric and symmetric vibrations bands. Thermal decomposition proceeds in a multistage way that results in metallic gold. Decomposition temperatures and thermal stability of the studied complexes depend on the length of the perfluorinated chain.