Syntheses, characterization of and studies on the

Phosphorus, Sulfur, and Silicon and the Related Elements

ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20

Syntheses, characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates Ertuğrul Gazi Sağlam, Sevcan Erden, Özgür Tutsak, Dilek Eskiköy Bayraktepe, Zehra Yazan Durmuş, Hakan Dal & Ahmet Ebinç To cite this article: Ertuğrul Gazi Sağlam, Sevcan Erden, Özgür Tutsak, Dilek Eskiköy Bayraktepe, Zehra Yazan Durmuş, Hakan Dal & Ahmet Ebinç (2017) Syntheses, characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates, Phosphorus, Sulfur, and Silicon and the Related Elements, 192:3, 322-329, DOI: 10.1080/10426507.2016.1238368 To link to this article: https://doi.org/10.1080/10426507.2016.1238368

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Accepted author version posted online: 21 Sep 2016. Published online: 28 Dec 2016.

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Date: 20 December 2017, At: 05:19

PHOSPHORUS, SULFUR, AND SILICON , VOL. , NO. , – http://dx.doi.org/./..

Syntheses, characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and -methoxyphenyl dithiophosphonates a ˘ Gazi Saglam ˘ Ertugrul , Sevcan Erdenb , Özgür Tutsaka , Dilek Eskiköy Bayraktepeb , Zehra Yazan Durmu¸sb , Hakan Dalc , a and Ahmet Ebinç

˘ Ankara, Turkey; c Department of Department of Chemistry, Bozok University, Yozgat, Turkey; b Department of Chemistry, Ankara University, Tandogan, ˘ Chemistry, Anadolu University, Yenibaglar, Eski¸sehir, Turkey

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a

ABSTRACT

ARTICLE HISTORY

Some 1,3-dithiadiphosphetane 2,4-disulfides (X2 P2 S4 , X: Fc, FcLR; X: CH3 O–C6 H4 –, LR) were allowed to react with alcohols to obtain dithiophosphonic acids (X(OR)PS2 H). These were converted to the corresponding ammonium salts. The salts were of the structures [Fc(OR)PS2 ]− [NH4 ]+ , R: 3-methyl-1-butyl- for I; 1-phenyl-1propyl- for II; 3-pentyl- for III; 3-phenyl-1-propyl- for IV and [CH3 O–C6 H4 (OR)PS2 ]− [NH4 ]+ , R: 3-methyl-1-butylfor V and 1-phenyl-1-propyl- for VI. To the best of our knowledge, all the compounds except V were prepared for the first time. The compounds synthesized were characterized by elemental analysis, NMR (1 H, 13 C, 31 P), MS, FTIR, and Raman spectroscopies. Electrochemical behaviors of I–VI at disposable pencil graphite electrode (PGE) were investigated by using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Adsorption and diffusion patterns of all the compounds on the PGE were also studied. Two electroactive groups were identified in the compounds I–IV and only one in V and VI. The ferrocenyl groups of I-IV were oxidized at around 0.4 V. The same compounds display a second, more intense CV band at 0.8 V. The corresponding band for the compounds V–VI appears at around 0.6 V with a much weaker intensity. It is suggested that the ferrocenyl group introduced into the structures stabilizes the radical species formed as the product of the oxidation of the dithiophosphonato group.

Received  April  Accepted  September  KEYWORDS

Ferrocenyl Lawesson reagent; Lawesson reagent; ferrocenyldithiophosphonate; thio-phosphorus compounds; cyclic voltammetry

GRAPHICAL ABSTRACT

Introduction The reaction of perthiophosphonic acid anhydride with alcohols and Grignard reagents is known to produce dithiophosphonic acids (DTPOA) and dithiophosphinic acids (DTPA), respectively.1–3 Due to their agricultural and industrial applications these compounds and their metal complexes are of interest. Among the applications are their use as additives to lubricant oils;4 antioxidant agents;5 extraction reagents for metals;6,7 insecticides and pesticides.8,9 Literature reports related to organo-dithiophosphonates and their metal derivatives are relatively rare compared to

organo-dithiophosphates and organo-dithiophosphinates. Excellent reviews setting background information for future studies have appeared.10,11 As to the ferrocenyl dithiophosphonates, a ferrocenyl perthiophoshonic acid anhydride, FcLR, the first example of the starting materials, was first explored by Woollins and coworkers.12 Similar to other perthiophoshonic acid anhydrides, such as Lawesson reagent, LR, FcLR reacts with alcohols to give ferrocenyl-dithiophosphonic acid (Fc-DTPOA). In recent years, several investigations on ferrocenyl dithiophosphonate derivatives have been carried out. Among these, work involving the

˘ Gazi Saglam ˘ CONTACT Ertugrul [email protected] Department of Chemistry, Faculty of Science and Art, Bozok University,  Yozgat, Turkey. Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss. Supplemental data for this article can be accessed on the publisher’s website at http://dx.doi.org/./.. ©  Taylor & Francis Group, LLC

PHOSPHORUS, SULFUR, AND SILICON

Scheme . Synthesis of perthiophosphonic acid anhydride through the reaction of H S and monothiophosphine dichlorides.

oxidative S-S coupling of the compounds is worth to bi mentioned.13–16 Electrochemical studies on ferrocenyl dithiophosphonates and other ferrocene bearing compounds have also appeared.15–20

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Results and discussion Perthiophosphonic acid anhydrides, namely, 1,3,2,4dithiadiphosphetane 2,4-disulfides, are important starting materials for the synthesis of organodithiophosphorus compounds.21,22 Two different routes are followed for the synthesis of the perthiophosphonic acid anhydrides. One route is based on the reaction of monothiophosphine dichlorides with hydrogen sulphide (Scheme 1). This approach is generally avoided because, the reaction of monothiophosphindichloride and hydrogen sulphide requires temperatures above 210°C and is violently exothermic.23 The second route is a milder one and based on the direct reaction of an electron donating aromatic compound with P4 S10 .24 This reaction is relatively safer and therefore the method of choice (Scheme 2). In this work, ammonium salts of four new ferrocenyl dithiophosphonic acids and a new dithiophosphonic acid were synthesized through the reaction of two perthiophosphonic acid anhydrides and alcohols. The procedure is summarized in Scheme 3. Spectroscopic studies IR and Raman spectra The prominent IR and Raman bands of the compounds are listed in Table 1. In the IR spectra the asymmetric and symmetric (PS) stretching signals (ν sym and ν asym ) of the compounds appear in the regions of 580–523 cm−1 and 650–625 cm−1 , respectively. In the Raman spectra, similar signals appear in the regions of 585–525 cm−1 and 657–625 cm−1 , respectively. In the IR spectra the characteristic ν N–H band is observed at between 3159 and 3080 cm−1 for IR and 3098–3113 cm−1 for Raman. The frequencies of the corresponding signals in the IR and the Raman spectra of the same compound are quite comparable as expected. All these values are in agreement with the literature.3,13,25,26 NMR spectra The 1 H, 13 C, and 31 P NMR data of the compounds are given in the experimental section. The numbering scheme for the protons is given in Figure 1. In the 1 H NMR spectra of the compounds I, II, III, and IV signals of the protons coded as subs-Fcring -C3H and subsFcring -C3 H are chemically equivalent in all the compounds

323

as expected. The signal of these protons are accidentally overlapped with those of the five-proton signals related to the unsubstituted ferrocene ring (unsbs-Fcring ). The integral area of the combined signal group corresponds to seven-protons as expected. In the 1 H NMR spectra of the compounds I, III and IV the protons subs-Fcring -C2H and -C2 H appear at around 4.6 ppm as multiplets. We suggest that the two protons are chemically nonequivalent; splitting by coupling to phosphorus into two and further splitting by coupling to the neighbouring protons so as to appear as a multiplet. The spin-spin coupling constants are not discernable. Compound II displays the same protons at 4.42 and 4.49 ppm as singlets, indicating that the two protons are nonequivalent. The two signals are too far apart (28 Hz) to be regarded as a 3 JPH coupling. We are inclined to comment that the couplings to phosphorus and also to the neighbouring protons are too small to be observable. Precise assigments of these two peaks were not done. The 1 H NMR signals of the C9H protons in II, III, and IV are obviously split by three-bond coupling to phosphorus, which is the case for similar structures.27–29 The signal of the proton C9H in compound I is splitted into two lines by coupling to phosphorus (3 JPH = 13.5 Hz) and further splitted by coupling to the geminal two protons (3 JHH = 6.8 Hz). Obviously the accidental magnitudes of the couplings gave rise to a pseudo quartet. The CH2 protons coded as C10H in compound II are diastereotopic as reflected by the doublet of multiplets located between 1.7 and 2.0 ppm. The phenyl protons of compounds II, IV, and VI appear at around 7.1 ppm as expected. The aromatic protons of compound VI and the phosphorus nucleus constitute an AA’MM’X spin system. The proton signals appear essentially in an AMX pattern, because JAM’ and JA’M are too small to be observable. The chemical shift assignment of the aromatic protons in this compound was made by referring to the magnitudes of the coupling constants to phosphorus. The orthoprotons appear to be splitted by 13.6 Hz by coupling to phosphorus (three-bond coupling) and further splitted by 8.7 Hz due to coupling to the geminal protons. The meta-protons interact with the phosphorus to the extent of a 2.7 Hz four-bond coupling. These findings agree well with the literature.3,30 In the 13 C NMR spectra of all compounds, the two-bond coupling constants 2 JPC for the P-O-C carbon atoms are observed to be in the narrow range of 8.8–7.4 Hz. The one bond couplings 1 JPC for C1 in compounds I, II, III, and IV are in the expected range (125.3, 123.5, 124.7, and 124.9 Hz, respectively). The corresponding coupling in compound VI is remarkably different (109.5 Hz), reflecting the difference between five- and six-membered aromatic rings. These values are in agreement with those reported for similar structures.29–31 In compounds I and VI the signals of the carbon atoms C2 and C2 coincide, indicating a chemical equivalence. The same applies to the signals of C3 and C3 . However, in compounds II and III the chemical shifts of C2 and C2 differ by 0.5–0.6 ppm (70.9 and 71.4 ppm for compound II and 70.6 and 71.2 ppm for compound III). The signals of the carbon atoms C3 and C3 are also different. This is probably due to the restricted rotation of the branched alkyl, aryl, and 3-pentyl groups. This comment is supported by the fact that the signals originating from C2 and C2 of compounds I, IV, and VI are chemically equivalent. Presumably, the alkyl groups with a straight chain at the proximity

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˘ E. G. SAGLAM ET AL.

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Scheme . Synthesis of perthiophosphonic acid anhydride.

Scheme . Synthesis reaction of the compounds.

of the phosphorus rotate freely. Two- and three-bond P-C coupling constants for compounds I, II, III, and IV are comparable to those reported for similar structures.27–31 The NMR signal related to the carbon atoms unsubs-Fcring in compounds I, II, III, and IV appears at ∼69 ppm, showing almost the same chemical shift as that of pure ferrocene.32 In compound VI the two-bond 31 P–13 C coupling for the aromatic carbon atoms is observed to be 13.6 Hz in the anisole group. For the same ring the three-bond 31 P–13 C coupling for the aromatic carbon atoms meta- to phosphorus is 14.9 Hz. The 2 JPC coupling for C6 is 7.8 Hz and 3 JPC for C7 is 8.2 Hz. These values compare well with those given in the literature.33,34

The 31 P NMR spectra of I, II, III, IV, and VI show singlets at 107.6, 103.3, 105.9, 108.2, and 105.1 ppm, respectively. Mass spectra The mass spectra of compounds I, II, III, IV, and VI display molecular ion peaks. The molecular ion peaks of compounds I, III, IV, and VI are also the principle peaks whereas in compounds II this is not the case. The natural abundance of isotopes is observable in the structure of the molecular ion signals. Signal patterns reported for similar compounds agree well with our signals.35

Table . Selected FTIR and Raman (R) data (cm− ) and assignment of the significant bands. ν(PS)(sym) Compound I II III IV VI

ν(PS)(asym)

ν (P-O-C)

ν (N-H)

IR

R

IR

R

IR

R

IR

R

    ;

    ;

    ;

 ;  ; ;

    

    

    

   ; —

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325

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Figure . Numbering scheme for compound I, II, III, IV, and VI.

Electrochemical behavior of the compounds The electrochemical behaviors as well as diffusion and adsorption properties of alkyl ferrocenyl- (I and III); alkyl- 4methoxyphenyl- (V); aryl- ferrocenyl (II and IV) and aryl4-methoxyphenyl (VI) dithiophosphonates were studied by using CV and SWV. 1.00 × 10−3 mol · L−1 solutions of the title compounds in a mixture of ethanol and BR buffer (1/1) were used for CV runs on disposable PGE at a scan rate of 0.100 Vs−1 . The CVs are displayed in Figures 2A and B. Solutions of I-IV adjusted to pH 2.0 gave rise to two well-defined oxidation peaks at the potentials of approximately 0.30 V and 0.80 V (Figures 2A and B). The CV peak at 0.30 V almost certainly corresponds to the oxidation of the ferrocenyl group as the voltammogram of the pure ferrocene indicates. Literature data obtained for ferrocenyl groups attached to conjugated backbones are comparable, despite some changes due to conjugations in those structures.36–38 To judge which electroactive group in the molecules is oxidized in the first oxidation step (Figures 2.A1-1 and 2.B1-1 inset), the CV of I-IV of ferrocene and of compounds V and VI (Figures 2A and B) were examined as pointed above. The higherpotential peaks presumably correspond to an oxidation on the P-S groups. Literature reports on the electrochemistry of some dithiophosphonato compounds indicate that an intermoleculer oxidative -P-S-S-P- coupling is the most likely alternative.15,16 As is evident in Figure 2(inset) the CV peak corresponding to the ferrocenyl group reflects a reversible process. This process is a well known one-electron oxidation.39 A comparison of the CV relating to compounds V–VI with those of I–IV suggests that the presence of the ferrocenyl group in the molecules not only gives rise to an additional oxidation peak but also causes at least a ten-fold increase in the intensity of the peak related to the P-S group (Figures 2A and B). Presumably, the ferrocenyl group introduced into the structures has a promoting effect on the formation of the radical species thought to have intervened in the oxidative coupling of the P–S groups. There is also some 0.2–0.3 V potential shift in the position of the peak towards more positive values (Table 2). The position of the ferrocenyl oxidation peaks in compounds I–IV is located at approximately 0.1 V higher potentials as

compared to the parent molecule, ferrocene (Figures 2A and B; Table 2). This means that the ferrocenyl group makes the oxidation of the P–S group more difficult. The Ep values are fairly small (0.1 V) which indicates that the redox reaction is quasireversible (Table 2). As examples, the number of electrons and protons involved in the electrochemical oxidation of the P–S group was tested by CV and SWV studies. The influence of the scan rate on the peak potential (Ep ) and also on the peak current (ip ) were investigated

Figure . A) Cyclic voltammograms of I, II, V, and ferrocene (each .×− mol.L− ) B) II, IV, VI, and ferrocene (each .×− mol.L− ) at pH ., scan rate . Vs− (inset ferrocenyl moiety).

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Table . The electrochemical data relating to the compounds I-VI (. × − mol · L− each at pH .) obtained in methanol + BR buffer (/) on PGE versus Ag/AgCl (M KCl). The scan rate is v =  mVs− . Compounds

Ipa (μA)

Ipa (μA)

Ipc (μA)

Epa (V)

Epa (V)

Epc (V)

Ep

I II III IV V VI Ferrocene

. . . . — — .

. . . . . . —

. . . . — — .

. . . . — — .

. . . . . . —

. . . . — — .

. . . . — — .

using 1.0×10−3 mol · L−1 solutions of compounds II and III in the 0.01–0.50 Vs−1 range. The slopes of the plots logip a versus logv, (about 0.5) also verify that the electrochemical characteristics of the compounds are not influenced by the adsorption phenomena (Figures 3A and B inset logip –logv).40,41 The peak potentials shift to more anodic values with increasing scan rate (Figures 3A and B for II and III) and as it was indicated before there is no cathodic peak at reverse scan at low scan rate. These findings support us to propose an irreversible oxidation mechanism for the compounds. When the scan rate varied from 0.010 to 0.50 Vs−1 a linear dependence of the peak potentials Ep (V) upon the logarithm of scan rate (log Vs−1 ) was found. The dependence is represented by the equations, Ep (V) = 0.048 × logυ + 0.8632 (with R2 = 0.9586) for II (Figure 3A) and Ep (V) = 0.071 × logυ + 0.8901 (with R2 = 0.9367) for III (Figure 3B). The theory of voltammetry predicts that the slope of the straight line Ep versus log Vs−1

is equal to 0.0296V/(nα), n being the number of electrons in the rate determining step and α the charge transfer coefficient.40 By applying this relation, (nα) values for II and III were calculated to be 0.62 and 0.42, respectively. SWV studies were also carried out on compounds II and III. The influence of the frequency (f, s−1 ) of the excitement signal on the peak potentials was investigated. The peak potentials shifted to more anodic values with increasing excitement frequency and the corresponding linear equations are as follows: Ep (V) = 0.047 × logf + 0.56 (with R2 = 0.9917) for II; Ep (V) = 0.079 × logf + 0.58 (with R2 = 0.9717) for III. Applying the equation “slope = 0.059/nα” given in the literature for this case,40,41 the values of (nα) were calculated to be 1.25 and 0.75 for II and III, respectively. Here n stands for the number of electrons in the overall reaction and therefore not in the rate determining step. These analyses indicate that the number of electrons involved are 2 for the both compounds. A similar analysis on the other compounds shows exactly the same behavior. The number of protons involved in the overall electrochemical process was studied using the CV runs in solutions of different pH values. For each compound, the Ep values at media of different pH were measured in the pH range 2.0–11.0. The change of Ep against the pH can be expressed by the linear equations, Ep (V) = 0.024 × pH + 0.93 (with R2 = 0.989751) for II; Ep (V) = 0.017 × pH + 0.84 (with R2 = 0.9907) for III. The ratio of the number of protons ( ∂) to that of electrons (n) the following equation was used.42 Ep = E0 +

RT ∂RT  +  [Ox] ln ln H − nF nF [Red]

In this equation Ep is peak potential in V (vs. Ag/AgCl); E0 is the standard peak potential; R is the ideal gas constant taken as 8.31 J/(mol · K); T is the absolute temperature (here, 298 ± 3 K); F is the Faraday constant; and [Ox] and [Red] are the molar concentrations of the oxidized and the reduced species. Use of this relation leads to the conclusion that one proton and two electrons take part in the overall electrode mechanism. A similar analysis for the other four compounds yielded similar results.

Conclusions

Figure . Influence of potential scan rate to peak currents and peak potentials (A) II, (B) III (inset: Potential versus the logarithm of scan rate and logip vs. logv).

Ammonium salts of four ferrocenyldithiophosphonates and two 4-methoxyphenyl dithiophosphonates were prepared. All of the compounds except one were synthesized and characterized for the first time. The characterizations were done by elemental analysis as well as MS, FTIR, RAMAN, 1 H, 13 C, and 31 P NMR spectroscopies. The 1 H NMR signal of the CH2 protons on the (α-ethyl)benzyl group of compound II is found to display diastereotopic nonequivalence. The structurally similar pairs of 1 H and 13 C nuclei on the cyclopentadienyl ring attached to phosphorus display chemical nonequivalence as well. Electrochemical studies on PGE reveal that compounds I-IV display two well defined CV peaks in the methanol-BR buffer mixture (1/1). The lower-potential peak belongs to the oxidation of the ferrocene group. The position of this peak is at some 0.1 V higher potentials compared to that of the parent molecule, ferrocene. The second peak is related to the oxidation of the P–S

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group. The former is a one electron process causing ferrocenyl moiety to get oxidized to the corresponding cationic species. The electrochemical reaction causing the latter peak involves two electrons and one proton. The introduction of the ferrocenyl group to the dithiophosphonate center appears to have caused a shift towards more positive potentials on the position of the oxidation peak of the P–S group. Interestingly, the intensity of this peak displays more than ten-fold increase as compared to other dithiophosphonates without ferrocenyl group.

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pH measurements were made with Thermo Orion Model 720A pH meter attached to an Orion combined-glass pH electrode (912600). Reagents and solutions

Experimental

Stock solutions of the title compounds (all being of 1.00 × 10−2 mol · L−1 concentration) were prepared in the Britton-Robinson buffer (BR). Working solutions (1.00 × 10−3 mol · L−1 ) were obtained by diluting the stock solution with the same buffer and the pH value of these solutions were adjusted to the desired values by dropwise addition of 0.2 mol · L−1 NaOH.

Materials and instruments

Voltammetric procedure

Analytical grade ferrocene, P4 S10 , xylene, 3-methyl-1-butanol, 1-phenyl-1-propanol, 3-pentanol, 3-phenyl-1-propanol, and LR were purchased from Merck and used directly without further purification. Benzene, n-hexane and diethyl ether were purchased from Merck and were distilled under nitrogen over a Na alloy with benzophenone ketyl indicator. FcLR and V were prepared as described in the literature.11,43 The LC/MS spectra were recorded with a Waters Micromass ZQ connected with Waters Alliance HPLC using ESI(+) method with the C-18 column. Melting points were measured with an Electrothermal 9200 melting point apparatus using a capillary tube. 1 H, 13 C{1 H}, and 31 P{1 H} NMR spectra were recorded with a Varian Mercury (Agilent) 400 MHz FT spectrometer in CD3 OD. SiMe4 (1 H, 13 C) and 85% H3 PO4 (31 P) were used as standards. Chemical shifts (δ) are given in ppm. IR spectra were recorded with a Perkin Elmer Spectrum Two Model FT-IR Spectrophotometer using the ATR method (200–4000 cm−1 ) and are reported in cm−1 units. All Raman spectra were measured in the range of 4000–100 cm−1 , at room temperature, using a Renishaw in-Via Raman microscope, equipped with a Peltier-cooled CCD detectors (−70°C). For Raman microscopy, a 50X objective was usually used and all the spectra were excited by the 785 line of a diode laser. Microanalyses were performed using a LECO CHNS-932 CHNS-O elemental analyzer. In the electrochemical part of the study all chemicals used in the preparation of BR solution, namely phosphoric acid (Riedel), boric acid (Riedel), acetic acid (Merck) and sodium hydroxide (Merck) were of analytical reagent grade. Doubledistilled deionized water was used in preparations of all the solutions. The Supplemental Materials contains sample 1H, 13C, 31P NMR, and mass spectra for products I–VI (Figures S1–S20).

For CV, 10.0 mL working solutions of the compounds in BR were placed in the electrochemical cell for each trial. The solution was deoxygenated by purging with purified argon (99.9%) for 2 min before the first running and for 30 s between successive runnings. The voltammograms were run in the positive direction by applying a scan from −0.4 to 1.40 V at PGE. All the experiments were carried out at room temperature. A newly polished and ethanol-rinsed PGE was used in each run. Each voltammetric signal was obtained as the mean of three successive runs.

Electrochemical apparatus Voltammetric measurements were made on a CH-instrument (CHI 660C) Electrochemical Analyzer with cell stand of C3. The pen-nibs (Tombow, Germany; 0.7 mm diameter), were used as disposable PGEs. A mechanical pencil (Rotring, Germany, T 0.7) was used as the holder for PGE. Electrical contact with the PGE was ensured by a copper wire attached to the metallic tip of the pencil. The PGE assembly was used as the working electrode. A platinum wire (BAS MW-1034) and Ag/AgCl electrode (stored in 3.0 mol · L−1 KCl solution; MF-2052 RE-5B) were used as the auxiliary and standard electrodes, respectively. All

Syntheses of the compounds General procedure for the synthesis of compounds I, II, III, and IV. A total 15–20 mL of benzene was boiled in a round-bottom flask under reflux and to the boiling liquid, 0.89 mmol (0.50 g) of FcLR was added. To this mixture, 1.78 mmol of alcohol (0.16 g of 3-methyl-1-butanol, 0.24 g of 1-phenyl-1-propanol, 0.16 g of 3pentanol or 0.24 g of 3-phenyl-1-propanol) was added dropwise. The reaction was carried on until all the solids were dissolved during which the colour changed from brick-red to brown. The mixture was left overnight at room temperature and then the solid impurities were filtered. The Fc-DTPOA in solution was treated with ammonia gas and the Fc-DTPOA-ammonium salt was obtained as a yellow-orange powder. This salt was filtered, washed with hot benzene, n-hexan and finally diethylether and dried in vacuum desiccator. Syntheses of VI. LR (0.50 g, 1.24 mmol) was mixed with 10– 15 mL of benzene in a round-bottomed flask (100 mL) and to this mixture a stoichiometric amount of alcohol (3-phenyl-1propanol), 0.34 g, 2.47 mmol was added dropwise. The mixture was heated to and kept at 60–70°C until complete dissolution of all solids, which takes 30 minutes roughly. The crude dithiophosphonic acid, DTPOA, was filtered, the filtrate was cooled to 5–10°C, and the acid was converted to compound VI by bubbling dry NH3 . The precipitated ammonium salt was filtered off as a colorless powder. This salt was washed with cold benzene and dried in air. Ammonium O-3-methyl-1-butyl(ferrocenyl) dithiophosphonate], I. 0.49 g, 72%. m.p. 149–151°C. Anal. Calcd. for, C15 H24 FeNOPS2 (385.31 g · mol−1 ): C, 46.76; H, 6.28; N, 3.64; S, 16.64. Found: C, 46.69; H, 6.19; N, 3.60; S, 16.59%.

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H NMR (CD3 OD): δ = 0.87 (d, 3 JHH = 6.7 Hz, 6H, C12H), 1.45 (dd, 3 JHH = 6.7 Hz, 3 JPH = 13.7 Hz, 2H, C9H), 1.71 (m, 1H, C11H), 3.92 (m, 2H, C10H), 4.26 (m, 7H, unsbs-Fcring overlapped with subs-Fcring C3H and C3 H), 4.57 (m, 2H, subs-Fcring C2H and C2 H). 13 C NMR (CD3 OD): δ = 21.6 (s, C12), 24.3 (s, C11), 39.1 (d, 2 JPC = 8.8 Hz, C9), 61.6 (d, 3 JPC = 7.0 Hz, C10), 69.2 (d, 3 JPC = 11.5 Hz, subs-Fcring -C3 and C3 coincide), 69.7 (s, unsubs-Fcring ), 71.2 (d, 2 JPC = 14.6 Hz, subs-Fcring -C2 and C2 coincide), 86.7 (d, JPC = 125.3 Hz, subs-Fcring -C1). 31 P NMR (CD3 OD): δ = 103.3. LC/MS: m/z 369.20 ([M–NH4 ]+ , 100%).

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Ammonium O-1-phenyl-1-propyl(ferrocenyl) dithiophosphonate], II. 0.57 g, 66%. m.p. 122–123°C. Anal. Calcd. for, C19 H24 FeNOPS2 (433.35 g · mol−1 ): C, 52.66; H, 5.58; N, 3.23; S, 14.80. Found: C, 52.49; H, 5.57; N, 3.21; S, 14.75%. 1 H NMR (CD3 OD): δ = 0.74 (t, 3 JHH = 7.3 Hz, 3H, –C11H), 1.9 (m, diastereotopic protons, 2H, H–C10-H), 4.21 (m, 7H, unsubsFcring H overlapped with subs-Fcring -C3H and C3 H), 4.49 (s, 1H, subs-Fcring C2H), 4.42 (s, 1H, subs-Fcring C2 H), 5.43 (m, 1H, C9H-), 7.20 (m, 5H, Ar–CH). 13 C NMR (CD3 OD): δ = 8.4 (s, C11), 30.9 (d, 3 JPC = 4.3 Hz, C10), 69.0 (d, 3 JPC = 11.5 Hz, subs-Fcring -C3), 69.1 (d, 3 JPC = 11.5 Hz, subs-Fcring -C3 ), 69.6 (s, unsubs-Fcring ), 70.9 (d, 2 JPC = 14.6 Hz, subs-Fcring -C2), 71.4 (d, 2 JPC = 14.7 Hz, subs-Fcring -C2 ), 78.1 (d, 2 JPC = 7.4 Hz, C9), 87.7 (d, JPC = 123.6 Hz, subs-Fcring -C1), 126.7 (s, C14), 127.2 (s, C13), 142.6 (d, 3 JPC = 4.0 Hz, C12). 31 P NMR (CD3 OD): δ = 107.6. LC/MS: m/z 455.01 ([M+Na]+ , 6%), 416.03 ([M–NH4 ]+ , 7%), 298.95 ([FcPS2 O+H]+ , 100%). Ammonium O-3-pentyl(ferrocenyl)dithiophosphonate], III. 0.53 g, 76%. m.p. 149–151°C. Anal. Calcd. for, C15 H24 FeNOPS2 (385.31 g · mol−1 ): C, 46.76; H, 6.28; N, 3.64; S, 16.64. Found: C, 46.72; H, 6.20; N, 3.63; S, 16.55%. 1 H NMR (CD3 OD): δ = 0.82 (d, 3 JHH = 7.5 Hz, 6H, C11H), 1.58 (m, 4H, C10H), 4.26 (m, 7H, unsubs-Fcring overlapped with subs-Fcring C3H and C3 H), 4.35 (m, 1H, C9H), 4.57 (m, 2H, subs-Fcring C2H and C2 H). 13 C NMR (CD3 OD): δ = 8.3 (s, –C11), 26.5 (d, 3 JPC = 4.0 Hz C10), 69.0 (d, 3 JPC = 11.5 Hz, subs-Fcring -C3 ), 69.2 (d, 3 JPC = 11.4 Hz, subs-Fcring -C3), 69.7 (s, unsubs-Fcring ), 70.6 (d, 2 JPC = 15.1 Hz, subs-Fcring -C2 ), 71.2 (d, 2 JPC = 14.5 Hz, subs-Fcring -C2), 77.2 (d, 2 JPC = 8.1 Hz, C9), 87.9 (d, JPC = 124.7 Hz, subs-Fcring -C1). 31 P NMR (CD3 OD): δ = 105.9. LC/MS: m/z 367.30 ([M–NH4 ]+ , 100%). Ammonium O-3-phenyl-1-propyl(ferrocenyl) dithiophosphonate], IV. 0.59 g, 69%. m.p. 122–12 3°C. Anal. Calcd. for, C19 H24 FeNOPS2 (433.35 g · mol−1 ): C, 52.66; H, 5.58; N, 3.23; S, 14.80. Found: C, 52.55; H, 5.57; N, 3.18; S, 14.71%. 1 H NMR (CD3 OD): δ = 1.85 (m, 2H, C10H), 2.65 (m, 2H, C11H), 3.92 (m, 2H, C9H), 4.27 (m, 7H, unsubs-Fcring overlapped with subs-Fcring C3H and C3 H), 4.59 (m, 2H, subs-Fcring C2H and C2 H), 7.15 (m, 5H, Ar–CH). 13 C NMR (CD3 OD): δ = 31.9 (s, C1), 32.3 (d, 3 JPC = 8.6, C9), 62.8 (d, 3 JPC = 7.0 Hz, C10), 69.3 (d, 3 JPC = 11.5 Hz, subs-Fcring -C3 and C3 coincide), 69.7 (s, unsubs-Fcring ), 71.3 (d, 2 JPC = 14.5 Hz, subs-Fcring -C2 and

C2 coincide), 86.7 (d, JPC = 124.9 Hz, subs-Fcring -C1), 125.2 (s, C15), 127.8 (s, C14), 128.1 (s, C13), 142.1 (s, C12). 31 P NMR (CD3 OD): δ = 108.2. LC/MS: m/z 417.18 ([M–NH4 ]+ , 100%). Ammonium O–3-phenyl-1-propyl-(4-methoxyphenyl) dithiophosphonate, VI. 0.39 g (91%). m.p. 118°C. Anal. Calcd. for C16 H22 NO2 PS2 (355.46 g · mol−1 ): C, 54.06; H, 6.24; N, 3.94; S, 18.04; found: C, 54.22; H, 6.20; N, 3.89; S, 18.10%. 1 H NMR (D2 O): δ = 1.84 (m, 2H, C7H), 2.53 (t, 3 JHH = 7.7 Hz, 2H, C8H), 3.74 (m, 2H, –C6H), 3.76 (m, 3H, OCH3 ), 6.88 (A-part of AA’MM’X, 4 JPH = 2.7 Hz (JAX ), N = JAM + JAM’ = 8.7 Hz, 2H, m-H); 8.01 (M-part of AA’MM’X, 3 JPH = 13.6 Hz (JMX ), N = 8.70 Hz, 2H, o-H), 7.04 (d, 3 JHH = 7.0 Hz, 2H, C10H), 7.13 (t, 3 JHH = 7.0 Hz, 1H, C12H), 7.20 (t, 3 JHH = 7.3 Hz, 2H, C11H). 13 C NMR (D2 O): δ = 31.8 (s, C7), 32.0 (s, C8), 55.4 (s, C5), 65.3 (d, 2 JPC = 7.8 Hz, C6), 113.5 (d, 3 JPC = 14.9 Hz, C3), 125.8 (s, C12), 128.3 (s, C11), 128.5 (s, C10), 132.1 (d, 2 JPC = 13.6 Hz, C6), 132.7 (d, 3 JPC = 109.5 Hz, C1), 141.5 (s, C9), 161.6 (d, 4 JPC = 2.9 Hz, C4). 31 P NMR (D2 O): δ = 105.1. LC/MS: m/z 340.00 ([M–NH4 ]+ , 100%).

Funding We gratefully acknowledge the financial assistance of The Scientific and Technological Research Council of Turkey (grant number TBAG 114Z091) and Ankara University Research Fund (Project No: 20050705094 and 13L4240009).

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