Skip to content
Publicly Available Published by De Gruyter January 17, 2019

Hydrogenation reaction pathways in chemistry of white phosphorus

Zufar N. Gafurov, Alexey A. Kagilev, Artyom O. Kantyukov, Oleg G. Sinyashin and Dmitry G. Yakhvarov

Abstract

Approaches for preparation of P–H bond containing derivatives directly from white phosphorus are summarized in this microreview. Transfer hydrogenation of P4 involving the activation and reaction of white phosphorus in the coordination sphere of transition metal complexes is a convenient and powerful route to the hydrogenated compounds. Electrochemical methods have also become popular in modern synthetic chemistry; these provide easy access to highly reactive intermediates, which can be selectively generated in situ and used for subsequent synthetic processes. These electrochemical routes provide efficient and environmentally safe methods for preparation of phosphorus derivatives bearing P–H bond. The mechanisms of the proposed processes and the nature of the intermediates formed in the overall electrochemical process are disclosed. The methods elaborated operate under the principals of “green chemistry” and can be considered as efficient alternatives to some classical pathways.

Introduction

Hydrogenation is one of the most fundamental transformations in organic synthesis and is widely used in both laboratory and industrial processes [1], [2], [3]. There are two main ways for hydrogenation reactions: direct hydrogenation with a pressure of H2 and transfer hydrogenation using a non-H2 hydrogen sources [4]. The main drawback of direct hydrogenation is the use of the hazardous pressurized H2 gas, whereas transfer hydrogenation implies the metal complex mediated addition of hydrogen to a molecule, which is much more convenient and powerful method to access various hydrogenated compounds. The hydrogenation reaction of elemental (white) phosphorus (P4), which is a common source for the production of different classes of inorganic and organic phosphorus compounds [5], [6], [7]. This is the one of the most commonly used and relatively straightforward ways to P–H derivatives that have high importance in different fields, including agriculture, human life and various industrial processes [8], [9], [10], [11], [12], [13]. However, the direct chemical hydrogenation of P4 is not easy and proceeds under very harsh conditions accompanied by the formation of flammable P–H-containing by-products and involves the handling of highly toxic phosphine gas under pressure. Thus, from this context, transition metal complexes and electrochemical techniques have been applied for direct hydrogenation of P4 molecule and discussed in this microreview.

Direct chemical hydrogenation of white phosphorus

Nitrogen and phosphorous are part of the same ‘family’ in the periodic table, group 15, also called the nitrogen group. There is one of the most important industrial process for agricultural community, the so called as the Haber–Bosch process which involves the production of synthetic ammonia by direct hydrogenation of nitrogen, using a revolutionary catalytic process combining N2 and H2 at high pressure [14], [15]. Nevertheless, the catalytic production of PH3 directly from white phosphorus and molecular hydrogen is still unknown. Although, there is some papers, where described the possibility of this process only under high H2 pressure at elevated temperature (>350°C), however, it is still the matter of debate [16], [17], [18]. As an alternative, the transition metal complexes and electrochemical techniques have been applied for the hydrogenation of P4. Metal-mediated reactions are one of the most often used techniques in the modern chemical science. A number of reports have mentioned the positive role of the metal in a variety of synthetic transformations where they act as reagents or catalysts [19], [20], [21], [22], [23], [24], [25]. The application of metal complexes for mild hydrogenation of white phosphorus is the most commonly applied method which allows control of the reactivity and selectivity of the process. Precisely designed unsaturated transition metal complexes, usually bearing bulky and strong electron donor ligands, allow both coordination of P4 and its functionalization [26], [27], [28], [29], [30], [31], [32], [33], [34], [35], [36], [37].

White phosphorus hydrogenation by transition metal hydrides

The first reaction of P4 with a transition metal complex was reported by Green and co-workers in 1974 (Scheme 1) [38]. They described the interaction between molybdenum dihydride [Cp2MoH2] (1), where (Cp=cyclopentadienyl, η5-C5H5) and P4 in toluene at 90°C, which leads to the formation of red crystals with molecular formula [Cp2Mo(η2-P2H2)] (2). The bonding behavior in 2 is similar to the related complex [Cp2Mo(C2H4)] bearing ethene molecule as a ligand. Later, Cannillo and co-workers have determined the structure of 2 by X-ray methods [39]. Unfortunately, the mechanism of the formation of 2 by transforming the MoH2 unit into the Mo(P2H2) is not fully understood, but Peruzzini et al. performed a good assumption on explanation of this interaction [29].

Scheme 1: The interaction of molybdenum dihydride (1) with P4. From Ref. [38].

Scheme 1:

The interaction of molybdenum dihydride (1) with P4. From Ref. [38].

The related reactions were also presented for the tantalum [40] and zirconium [41] hydrides. In case of tantalum trihydride [Cp2TaH3] (3) (Scheme 2a) the process leads to the formation of hydridodiphosphene [Cp2Ta(H)(η2-P2H2)] (4). The structure of 4 verified by X-ray method, which confirms the presence of a transoid diphosphene unit coordinated to the tantalum center. However, no mechanistic interpretation has been presented by the authors. Unlike to 1 and 3, zirconium hydride [Cp*2ZrH2] (5) in the reaction with white phosphorus did not undergo the desired insertion into the Zr–H, but gave [Cp*2Zr(η2-P4)] (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl, η5-C5Me5) with the further reductive elimination of H2 (Scheme 2b) [42]. A completely different reaction takes place by using a sterically more hindering zirconium complex [{Cp*(η5-C5H4tBu)ZrH2}2] (7) (Scheme 2c) [41]. The molecular structure of obtained dizirconium complex [{Cp*(η5-C5H4tBu)Zr}2(μ,η2:2-P4H2)] (8), contains a tetraphosphorus anionic ligand [P4H2]4ˉ tethering two zirconocene units.

Scheme 2: The interaction of tantalum (a) and zirconium hydrides (b and c) with P4.

Scheme 2:

The interaction of tantalum (a) and zirconium hydrides (b and c) with P4.

More details on the chemistry of transition metal complexes containing P–H bonds can be found in the excellent review of Peruzzini and co-workers, published in 2001 [29], which specifically high-lights the possibility of establishing one or more P–H bonds in a transition metal center by hydrogenation of white phosphorus or polyphosphorus ligands. Therefore, in present paper we will discuss only several most recent examples of metal-mediated hydrogenation of white phosphorus.

However, it is worth to mention the interesting reaction of rhodium and iridium trihydrides [(triphos)MH3] (M is Rh (9) or Ir (10), triphos=1,1,1-tris(diphenylphosphinomethyl)ethane) [43], [44] with P4 in THF at about 70°C under nitrogen atmosphere (Scheme 3) [45], [46]. It was found, that the first step of this interaction is the generation of the transient [(triphos)MH] complex by thermal reductive elimination of H2 from starting complexes. Then, the oxidative addition of P4 to generated [(triphos)MH] takes place, yielding the [(triphos)MH(η12-P4)] (M== Rh (11), Ir (12)). After that, the intramolecular migration of the hydride ligand from metal to phosphorus leads to the formation of new rhodium (13) and iridium (14) complexes bearing η12-HP4 ligand, acting as a six-electron donor towards the (triphos)M fragment. And as a final step, the addition of H2 to the HP4 ligand with concomitant P–P bond cleavage eliminates the phosphine PH3 and cyclo-P3 complexes [(triphos)M(η3-P3)] (M== Rh (15), Ir (16)) (Scheme 3) [47].

Scheme 3: Mechanism for the stoichiometric hydrogenation of P4 promoted by [(triphos)MH3] (M=Rh (3), Ir (4)) complexes.

Scheme 3:

Mechanism for the stoichiometric hydrogenation of P4 promoted by [(triphos)MH3] (M=Rh (3), Ir (4)) complexes.

It is interesting to note, that it is possible to form PH2R compounds by direct transfer of an organic group from an organotransition metal derivative to a metal-activated tetraphosphorus molecule. Thus, alkyl and aryl rhodium complexes [(triphos)RhR(η2-C2H4)] (R=H, (17); Me, (18); Et, (19); Ph, (20)), labilized by ethylene, can react with P4 under mild conditions (THF, −20°C) [48], [49]. This interaction proceeds through the formation of rhodium (III) complexes [(triphos)Rh(η2:1-P4R)] (R=Me, (21); Et, (22); Ph, (23)). The reaction with the hydrido-ethylene complex 17 leads to the ethylphosphido species 22 by the transferring the generated ethyl ligand to the activated P4 unit. The next step is the formation of alkyl or arylphosphines PH2R in moderate yields and cyclo-P3 complex 15 in the reaction of 21–23 with hydrogen. (Scheme 4).

Scheme 4: Formation of PH2R (R=Me, Et, Ph) in the reaction of alkyl and aryl rhodium complexes 18–20 and P4.

Scheme 4:

Formation of PH2R (R=Me, Et, Ph) in the reaction of alkyl and aryl rhodium complexes 18–20 and P4.

The cyclopentadienyl ruthenium complexes [CpRu(L)2Cl], where L==PPh3 (24); ½ dppe (1,2-bis(diphenylphosphino)ethane) (25); PMe3 (26) under argon in the mixture of CH2Cl2 and THF reacts with one equivalent of P4 (with 0,5 equivalent in case of 26) in the presence of chloride scavengers (TlPF6 or AgCF3SO3), leading to precipitation of TlCl or AgCl and coordination of the P4 molecule to form the [CpRu(L)21-P4)]Y (L=PPh3, Y==PF6 (27a); L==PPh3, Y==CF3SO3 (27b); L=½ dppe, Y==PF6 (28a); L=½ dppe, Y==CF3SO3 (28b)) complexes in good yield (>95%) (Scheme 5) [50] and [{CpRu(PMe3)2}2(μ,η1:1-P4)}](PF6)2 (29) in case of complex 26 [51]. The complex 27a is able to react with a second equivalent of [CpRu(PPh3)2Cl] forming in quantitative yield the diruthenated-tetraphosphorus complex [{CpRu(PPh3)2}2(μ,η1:1-P4)}](PF6)2 (30) whose bimetallic nature was confirmed by X-ray crystallography. It was found, that the reaction of 27a and 28a with water yields the highly stable PH3 complexes [CpRu(L)2(PH3)]PF6 (L==PPh3, (31); ½ dppe, (32)). The structure of 31 is also determined by X-ray methods. The complexes 29 and 30 react are capable react with water or methanol to form a mixture of the compounds: free phosphorous acid (17%), [CpRu(L)2(PH3)]+ (31 and 33), ruthenium cationic species [CpRu(L)2{PH(OH)2}]+ (34) and [CpRu(L)2{P(OCH3)3}]+ (35), diphosphine complex [{CpRu(L)2}2(μ,η1:1-P2H4))]2+ (36 and 37) and [CpRu(L)2{P(OH)3}]+ (38 and 39) as shown in the Scheme 5 [51], [52].

Scheme 5: The reactivity of cyclopentadienyl ruthenium complexes [CpRu(L)2Cl] (L=PPh3 (24); ½ dppe (25), PMe3 (26)) with P4.

Scheme 5:

The reactivity of cyclopentadienyl ruthenium complexes [CpRu(L)2Cl] (L=PPh3 (24); ½ dppe (25), PMe3 (26)) with P4.

This result shows that using the principles of coordination chemistry of transition metals and white phosphorus as ligand may be one of the simple pathways for its hydrogenation. However, these processes cannot be considered from the view point of the industrial interest as only one molecule of white phosphorus (P4) can be hydrogenated by one metal complex and the process does not operate in a catalytic mode.

White phosphorus hydrogenation by other hydrides

Bhattacharyya et al. have demonstrated the possibility of the hydrogenation of P4 using various hydride sources, such as MBH4 (M==Li or Na) and super-hydride LiBEt3H [53]. In a first approach, NaBH4 or LiBH4 (12 equiv.) was reacted with P4 (1 equiv.) in different solvents (Scheme 6). It was found, that depending on used solvent various hydrogenated phosphorus derivatives were obtained. Thus, in EtOH, only a mixture of PH3 and P2H4 were formed upon heating at 70°C (47% decent combined 31P NMR yield). In case of using n-butylamine as a solvent at room temperature only compounds 40a (M==Li) and 40b (M==Na) were obtained in good 31P NMR yields (74 and 70%, respectively). Nevertheless, these results highlight the potential of main group hydride sources to form P–H bonds from P4.

Scheme 6: Reactivity of P4 with MBH4 (M=Li, Na). From Ref. [53].

Scheme 6:

Reactivity of P4 with MBH4 (M=Li, Na). From Ref. [53].

In the reaction of white phosphorus with super-hydride LiBEt3H under optimized conditions the formation of LiPH2(BEt3)2 (41) with 61% of yield was observed as a broad triplet at −98 ppm by 31P NMR (triplet, 1JP−H=260 Hz) (Scheme 7a). The formation of the LiPH2 moiety has been proved by the reaction with LiBEt3D, as a result of which the deuterated analog of 41 was obtained (containing the LiPD2 moiety). It is interesting to note, that compound 41 after 4 h being under vacuum loses stabilizing BEt3 moiety and decompose to LiPH2(BEt3) (42) (triplet in the 31P NMR spectrum at −186 ppm) and LiPH2 (43) (−294 ppm in the 31P NMR spectrum) (Scheme 7b) [54]. Authors have investigated the reactivity of compound 41. Thus, in the reactions with H+ sources, including MeOH, EtOH, nBuNH2, and H2O, the quantitative formation of PH3 was observed (Scheme 7c). It should be noted, that in case of interaction of LiBEt3D and D2O the formation of only PD3 was found [53].

Scheme 7: Reactivity of P4 with super-hydride LiBEt3H (a) and reactivity of LiPH2(BEt3)2 (b and c).

Scheme 7:

Reactivity of P4 with super-hydride LiBEt3H (a) and reactivity of LiPH2(BEt3)2 (b and c).

White phosphorus protonation by Brønsted superacid

Recently in a common work of the groups of Riedel and Müller a possibility of direct protonation of P4 molecule by the Brønsted superacid H[Al(OTeF5)4](solv) has been described [55]. Theoretical studies on the protonation of P4 have variably predicted that protonation happens either at the apex of the P4-tetrahedron or on the edge of the tetrahedron, forming a three-center two-electron P–H–P bond in [P4H]+. The reaction product [P4H] [Al(OTeF5)4] was obtained as a temperature-, moisture- and oxygen-sensitive salt. It shows a clean low-temperature proton-coupled 31P NMR spectrum with two equally intense signals at −481.7 and −405.8 ppm with a weak roof effect.

Electrochemical hydrogenation of white phosphorus

The development of new industrially applicable synthetic methods for preparation of organoelement compounds and functional materials is one of the key tasks of the modern chemical science [12]. In this context, the application of the electrochemical techniques is a highly efficient alternative to classical synthetic procedures due to relatively cheap and the most convenient type of energy [56], [57], [58]. Electrochemistry can be considered as a “green” technique since it uses electrons as reagents and avoids the formation of by-products. The electrochemical processes have been already successfully applied for preparation of different classes of practically important chemical compounds [59]. Recently our group published a review described the electrode reactions of element (white) phosphorus and phosphine PH3 [60]. Therefore, in the present microreview we have summarized the investigations on this topic, focusing on the mechanistic insides of the processes for direct electrochemical hydrogenation of white phosphorus.

Electrochemical oxidation and reduction processes

The electrochemical oxidation of white phosphorus mostly leads to the formation of various oxyacids, such as phosphoric H3PO4 and phosphorous H3PO3 acids. The addition of some organic solvents (such as benzene or chloroform) allows to increase the P4 volume concentration and increase the efficiency of the electrochemical process. However, less attention has been paid to the electrooxidation of P4 due its easy chemical oxidation on air by molecular oxygen.

The direct electrochemical production of different phosphorus oxyacids from white phosphorus in MeCN or DMF is also known [61], [62], [63], [64], [65], [66], [67], [68], [69]. The simultaneous in situ generation of alkoxy ions from alcohol (nucleophile) on GC or platinum cathode and oxidation of halide from the supporting electrolyte salt with further formation of electrophiles on anode and their reaction with P4 is main advantage of this method (Scheme 8). The result of this interactions is the formation of various phosphorus oxyacids and organic phosphorus derivatives, mainly phosphates, pyrophosphates, phosphites etc [70].

Scheme 8: The electrochemical system for synthesis of phosphates and phosphorus oxyacids starting from white phosphorus P4.

Scheme 8:

The electrochemical system for synthesis of phosphates and phosphorus oxyacids starting from white phosphorus P4.

It has been shown, that depending on the experimental conditions, such as solvent (usually water or its mixtures with alcohol), electrode materials, temperature and pH, the electrochemical process can be adjusted to give predominantly desired products [71], [72], [73], [74], [75], [76]. Thus, the first step of the electrochemical reduction of white phosphorus on the cathode is the formation of high reactive radical anion [P4]˙ˉ at the first electron transfer, which is irreversible process taking place at Еpred=−2.25 V (vs Ag/AgNO3, 0.01 M in MeCN) (Fig. 1).

Fig. 1: CV curve (cathodic part) recorded from a solution containing white phosphorus (0.01 M) in EtOH on GC-electrode in the presence of 0.1 M nBu4NBF4 (CV curve was recorded at the first scan: from 0.00 V to −2.60 V and back to 0.00 V, EpC1=−2.33 V vs Ag/AgNO3, 0.01 M). From Ref. [60].

Fig. 1:

CV curve (cathodic part) recorded from a solution containing white phosphorus (0.01 M) in EtOH on GC-electrode in the presence of 0.1 M nBu4NBF4 (CV curve was recorded at the first scan: from 0.00 V to −2.60 V and back to 0.00 V, EpC1=−2.33 V vs Ag/AgNO3, 0.01 M). From Ref. [60].

Fast protonation of the electrochemically generated radical anion [P4]˙ˉ takes places in the process carried out in protic media, resulting in cleavage of P–P bonds in white phosphorus tetrahedron and formation of P–H derivatives, such as PH3. A number of publications on the electrochemical hydrogenation of elemental (white) phosphorus using various types of cathodes describes the possibility of in situ generation of highly pure PH3 directly from P4. Gaseous phosphine can be collected and used in synthesis of desired organophosphorus derivatives.

The yields of PH3 are varied in the range of 60–83% on the lead taken as the working electrode in 15–25% NaOH aqueous solution at 70–100 °C [77], [78], [79], [80]. In a classical chemical process, operating without electrochemistry under these circumstances, allows obtaining a mixture of products: hypophosphite (50%), phosphite (25%) and phosphine PH3 (25%) as well as molecular hydrogen. Nevertheless, there is a way to increase the yields of electrochemically generated PH3 using special construction of the electrochemical apparatus with turbulent flow of white phosphorus emulsion in electrolyser has been described.

A recent study describes the selective electrochemical transformation of white phosphorus into H3PO (Scheme 9) [81]. The electrochemical generation of PH3 from white phosphorus on the cathode is the first step of the process. The second step includes mild anodic oxidation of PH3 to H3PO. The use of lead electrode as a cathode and zinc anode was found as the best combination for high yield production of H3PO. However, PH3 and H3PO2 are also present in the reaction mixture as their formation is the result of disproportionation process of the electrochemically generated H3PO (Fig. 2). It is interesting to note, that no H3PO formation was observed by replacing of zinc electrode by GC-electrode even in the presence of specially added Zn2+ ions (from ZnCl2). Thus, it was concluded that the nature of the sacrificial anode has strong influence of the formation of H3PO in the electrochemical conditions [82]. Moreover, recent study of the reactivity of the electrochemically generated H3PO has demonstrated a high synthetic potential of this intermediate which can be applied for the synthesis of organophosphorus compounds [83].

Scheme 9: Electrochemical generation of H3PO in acidic EtOH/H2O solution from P4. From Ref. [81].

Scheme 9:

Electrochemical generation of H3PO in acidic EtOH/H2O solution from P4. From Ref. [81].

Fig. 2: 31P{1H} NMR (top) and 31P NMR (bottom) spectra (D2O, RT) of an acidic EtOH/H2O solution of P4 after electrolysis (30 min). From Ref. [81].

Fig. 2:

31P{1H} NMR (top) and 31P NMR (bottom) spectra (D2O, RT) of an acidic EtOH/H2O solution of P4 after electrolysis (30 min). From Ref. [81].

Mechanistic insights

Lead was selected as the electrode material due to its high overvoltage of molecular hydrogen evolution and high efficiency in the process of the electrochemical reduction of white phosphorus leading to formation of phosphine PH3 as the major product. The monitoring of the lead electrode surface during the electrochemical processes using methods of 31P NMR spectroscopy and scanning electron microscopy (SEM) supplied with X-ray fluorescence analysis (RFA) allows concluding, that the role of the lead cathode in the process of the production of PH3 isn’t limited as the electrode for Faraday process, but also strongly involved in electrochemical reaction [60]. Thus, the surface of the lead electrode before the experiments is shown on Fig. 3. After applying of the cathodic potential to the lead in ethanol/HCl/water solution strong modification of the lead surface by growing of the lead crystals was observed (Fig. 3).

Fig. 3: Pb-electrode surface before (a) and after (b) the electrolysis in ethanol/HCl/water solution (magnification=5000 times). From Ref. [60].

Fig. 3:

Pb-electrode surface before (a) and after (b) the electrolysis in ethanol/HCl/water solution (magnification=5000 times). From Ref. [60].

It is interesting to note, that no changes on the mass of the lead electrode was found. Moreover, the repeating of the experiment without applying of electric current showed less changes on the surface of the lead plate with increasing of its mass to 0.2–0.3% by formation of lead chloride (Scheme 10a). The differences can be explained by cathodic protection of lead in case of electrochemical process with consumption of electric current by reduction of the protons to hydrogen radicals (Scheme 10b). The formation of lead hydrides species is reversible reaction proceeding with their decomposition leading to regeneration of the metallic lead and radical hydrogen [84], reflecting in the formation of Pb-crystals and modifying of the electrode surface without changing of the overall mass in electrochemical conditions.

Scheme 10: The reactions on the lead surface in ethanol/HCl/water solution (a and b) and electrochemical reduction of P4 on Pb-electrode (c).

Scheme 10:

The reactions on the lead surface in ethanol/HCl/water solution (a and b) and electrochemical reduction of P4 on Pb-electrode (c).

The strong modification of the electrode surface was observed also after performing the electrolysis in the present of white phosphorus (Fig. 4). According to RFA and 31P NMR analysis no phosphorus derivatives has been found on the lead plate. Nevertheless, the influence of white phosphorus on the surface processes is obvious. It is interesting to note, that formation of PH3 is impossible in case of replacing of the lead by platinum as a cathode (only formation of molecular hydrogen was observed). This allows to conclude, that lead is the best electrode material for the process of production of PH3 due to formation of lead hydrate species as hydrogen radical “storage”, which doesn’t lead to formation of molecular hydrogen. Obviously, the presence of high-reactive newly born hydrogen so-called “nascent” during the electrochemical process is obligatory (Scheme 10b and c). In the presence of white phosphorus, these high-reactive intermediates react with white phosphorus tetrahedral molecules forming phosphine PH3 as the final product of the electrochemical process. All obtained results demonstrate that the surface of lead electrode is strongly involved in the process of white phosphorus electrochemical reduction to phosphine PH3.

Fig. 4: Pb-electrode surface after the electrolysis in ethanol/HCl/water/P4 solution (magnification=5000 times). From Ref. [60].

Fig. 4:

Pb-electrode surface after the electrolysis in ethanol/HCl/water/P4 solution (magnification=5000 times). From Ref. [60].

It is interesting to note, that in case of using the spin trapping reagent – α-phenyl-tert-butyl nitrone (PBN) (44) – the strong decreasing of PH3 formation was observed. This experiment allows concluding the radical nature of the overall electrochemical process. The performed in situ EPR-spectroelectrochemical study shows the formation of a PBN/H˙ (45) spin-adduct (Scheme 11). The EPR spectrum of this spin adduct is shown on Fig. 5. The hyperfine structure involves coupling from nitrogen (tree lines with 1.524 mT coupling constant) and from two α-hydrogen atoms gives additional triplets (0.856 mT coupling constant) [60].

Scheme 11: The formation of a spin-adduct of PBN (45) with hydrogen radical. From Ref. [60].

Scheme 11:

The formation of a spin-adduct of PBN (45) with hydrogen radical. From Ref. [60].

Fig. 5: EPR spectrum of the PBN/H˙ (45) spin-adduct obtained in CH3CN containing nBu4NBF4 (0.1 M) on Pb-electrode (g=2.001, N: 1.524 mT, 2H(CH2): 0.856 mT). From Ref. [60].

Fig. 5:

EPR spectrum of the PBN/H˙ (45) spin-adduct obtained in CH3CN containing nBu4NBF4 (0.1 M) on Pb-electrode (g=2.001, N: 1.524 mT, 2H(CH2): 0.856 mT). From Ref. [60].

Thus, based on these experiments some conclusions about the electrochemical processes involving white phosphorus can be summarized. The reaction mechanism (Scheme 10) involves the electrochemical generation of hydrogen radicals, stabilized by the formation of lead hydride species, which are able to react with white phosphorus tetrahedron opening P–P and forming new P–H bonds. The overall surface process leads to formation of phosphine PH3 as the major product of the electrochemical process. The lead surface is strongly involved, modified, but is not consumed, in electrochemical process. The electrode reactions of white phosphorus are important for more deep understanding of P4 reactivity and elaboration of new ecologically safe and waste-free technologies of phosphorus compounds production. Undoubtedly, the use of electric current as a power source and electron as “universal” and “inexhaustible” reagent seems very promising.

Conclusions

So far, no catalytic production of PH3 from white phosphorus and hydrogen has been described, but as an attractive alternative to direct hydrogenation, transfer hydrogenation involving non-H2 hydrogen sources is a rapidly growing field from the viewpoint of development of sustainable chemistry including economy consideration. A number of transition metal complexes have been successfully applied for this purpose. The results show that the molecule of white phosphorus exhibits rich and intriguing coordination abilities. It is also known the potential of main group hydride sources to form P–H bonds from white phosphorus. The use of the electrochemical techniques offers many interesting opportunities for the direct application to the synthesis of PH compounds and organophosphorus derivatives. Moreover, coupling electrochemistry with other analytic techniques (EPR, NMR, SEM, RFA, etc.) and careful analysis of the surface processes allows more insight into the mechanism of the process. The preparative electrochemistry operating the principles of “green chemistry” are also very important from the view point of possible modernization of the current industrial technology.


Article note

A collection of invited papers based on presentations at the 22nd International Conference on Phosphorous Chemistry (ICPC-22) held in Budapest, Hungary, 8–13 July 2018.


Funding source: Russian Science Foundation

Award Identifier / Grant number: 18-13-00442

Funding statement: This work is financially supported by the Russian Science Foundation (project 18-13-00442).

References

[1] L. Cerveny. Catalytic Hydrogenation, Elsevier, Amsterdam (1986).Search in Google Scholar

[2] J. G. de Vries, C. J. Elsevier. The Handbook of Homogeneous Hydrogenation, Wiley-VCH, Weinheim (2007).10.1002/9783527619382Search in Google Scholar

[3] P. G. Andersson, I. J. Munslow. Modern Reduction Methods, pp. 1–501, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim (2008).10.1002/9783527622115Search in Google Scholar

[4] D. Wang, D. Astruc. Chem. Rev.115, 6621 (2015).10.1021/acs.chemrev.5b00203Search in Google Scholar PubMed

[5] F. A. Cotton, G. Wilkinson. Advanced Inorganic Chemistry, pp. 386, John Wiley & Sons, New York (1988).Search in Google Scholar

[6] Studies in Inorganic Chemistry 20. Phosphorus. An outline of its Chemistry, Biochemistry and Technology, 5 ed., D. E. C. Corbridge (Ed.), pp. 1208, Elsevier (Science B. V.), Amsterdam – Lausanne – New York – Oxford – Shannon – Tokyo (1995).Search in Google Scholar

[7] K. B. Dillon, F. Mathey, J. F. Nixon. Phosphorus: The Carbon Copy, Wiley, Chichester (1998).Search in Google Scholar

[8] D. Cordell, J-O. Drangert, S. White. Glob. Environ. Chang.19, 292 (2009).10.1016/j.gloenvcha.2008.10.009Search in Google Scholar

[9] A. I. Razumov. Usp. Khim.26, 975 (1957).Search in Google Scholar

[10] B. A. Trofimov, S. N. Arbuzova, N. K Gusarova. Rus. Chem. Rev.68, 215 (1999).10.1070/RC1999v068n03ABEH000464Search in Google Scholar

[11] F. Mathey. Angew. Chem. Int. Ed.42, 1578 (2003).10.1002/anie.200200557Search in Google Scholar PubMed

[12] M. Peruzzini, L. Gonsalvi. Phosphorus compounds: Advanced tools in catalysis and material sciences. Catalysis by Metal Complexes, pp. 487, Springer, Dordrecht-Heidelberg-London-New York (2011).10.1007/978-90-481-3817-3Search in Google Scholar

[13] The U.S. chemical industry. Technology vision 2020, pp. 75, American Chemical Society, Washington (1996).Search in Google Scholar

[14] M. Appl. The Haber–Bosch Process and the Development of Chemical Engineering, pp. 29–54, A Century of Chemical Engineering, New York (1982).10.1007/978-1-4899-5289-9_3Search in Google Scholar

[15] M. Appl. Ammonia, Wiley-VCH, Weinheim (1999).10.1002/9783527613885Search in Google Scholar

[16] J. W. Mellor. A Comprehensive Treatise on Inorganic and Theoretical Chemistry, pp. 782, Longmans, Green and Co., London (1958).Search in Google Scholar

[17] V. Ipatieff, V. Nikolajeff. Ber. Dtsch. Chem. Ges. 59, 595 (1926).10.1002/cber.19260590337Search in Google Scholar

[18] A. Delique. Bull. Soc. Chim. Fr. 53, 603 (1933).Search in Google Scholar

[19] I. F. Sakhapov, Z. N. Gafurov, V. M. Babaev, V. A. Kurmaz, R. R. Mukhametbareev, I. Kh. Rizvanov, O. G. Sinyashin, D. G. Yakhvarov. Russ. J. Electrochem.51, 1061 (2015).10.1134/S1023193515110142Search in Google Scholar

[20] Z. N. Gafurov, I. F. Sakhapov, V. M. Babaev, A. B. Dobrynin, V. A. Kurmaz, K. E. Metlushka, I. K. Rizvanov, G. R. Shaikhutdinova, O. G. Sinyashin, D. G. Yakhvarov. Russ. Chem. Bull.66, 254 (2017).10.1007/s11172-017-1725-8Search in Google Scholar

[21] Z. N. Gafurov, A. O. Kantyukov, A. A. Kagilev, A. A. Balabaev, O. G. Sinyashin, D. G. Yakhvarov. Russ. Chem. Bull.66, 1529 (2017).10.1007/s11172-017-1920-7Search in Google Scholar

[22] E. C. Hansen, C. Li, S. Yang, D. Pedro, D. J. Weix. J. Organomet. Chem.82, 7085 (2017).10.1021/acs.joc.7b01334Search in Google Scholar PubMed PubMed Central

[23] Z. N. Gafurov, A. A. Kagilev, A. O. Kantyukov, A. A. Balabaev, O. G. Sinyashin, D. G. Yakhvarov. Russ. Chem. Bull.67, 385 (2018).10.1007/s11172-018-2086-7Search in Google Scholar

[24] Z. N. Gafurov, L. I. Musin, I. F. Sakhapov, V. M. Babaev, E. I. Musina, A. A. Karasik, O. G. Sinyashin, D. G. Yakhvarov. Phosphorus, Sulfur Silicon Relat. Elem.191, 1475 (2016).10.1080/10426507.2016.1212045Search in Google Scholar

[25] D. G. Yakhvarov, A. F. Khusnuriyalova, O. G. Sinyashin. Organometallics. 33, 4574 (2014).10.1021/om500100qSearch in Google Scholar

[26] A. P. Ginsberg, W. E. Lindsell. J. Am. Chem. Soc.93, 2082 (1971).10.1021/ja00737a059Search in Google Scholar

[27] A. P. Ginsberg, W. E. Lindsell, K. J. McCullough, C. R. Sprinkle, A. J. Welch. J. Am. Chem. Soc. 108, 403 (1986).10.1021/ja00263a010Search in Google Scholar PubMed

[28] Y. A. Dorfman, M. M. Aleshkova, G. S. Polimbetova, L. V. Levina, T. V. Petrova, R. R. Abdreimova, D. M. Doroshkevich. Russ. Chem. Rev. 62, 877 (1993).10.1070/RC1993v062n09ABEH000051Search in Google Scholar

[29] M. Peruzzini, I. de los Rios, A. Romerosa, F. Vizza. Eur. J. Inorg. Chem. 3, 593 (2001).10.1002/1099-0682(200103)2001:3<593::AID-EJIC593>3.0.CO;2-NSearch in Google Scholar

[30] B. M. Cossairt, B. M. Piro, C. C. Cummins. Chem. Rev.110, 4164 (2010).10.1021/cr9003709Search in Google Scholar

[31] M. Scheer, G. Balázs, A. Seitz. Chem. Rev.110, 4236 (2010).10.1021/cr100010eSearch in Google Scholar

[32] M. Caporali, L. Gonsalvi, A. Rossin, M. Peruzzini. Chem. Rev.110, 4178 (2010).10.1021/cr900349uSearch in Google Scholar

[33] K. M. Armstrong, P. Kilian. Eur. J. Inorg. Chem.13, 2138 (2011).10.1002/ejic.201100046Search in Google Scholar

[34] M. Caporali, P. Barbaro, L. Gonsalvi, A. Ienco, D. Yakhvarov, M. Peruzzini. Angew. Chem. Int. Ed.47, 3766 (2008).10.1002/anie.200800470Search in Google Scholar

[35] M. Peruzzini, R. R. Abdreimova, Y. Budnikova, A. Romerosa, O. J. Scherer, H. Sitzmann. J. Organomet. Chem.689, 4319 (2004).10.1016/j.jorganchem.2004.05.041Search in Google Scholar

[36] M. Peruzzini, L. Gonsalvi, A. Romerosa. Chem. Soc. Rev.34, 1038 (2005).10.1039/b510917eSearch in Google Scholar

[37] D. G. Yakhvarov, S. V. Kvashennikova, O. G. Sinyashin. Russ. Chem. Bull.62, 2472 (2013).10.1007/s11172-013-0358-9Search in Google Scholar

[38] J. C. Green, M. L. H. Green, G. E. Morris, J. Chem. Soc. Chem. Commun. 212 (1974).10.1039/C39740000212Search in Google Scholar

[39] E. Cannillo, A. Coda, K. Prout, J.-C. Daran. Acta Crystallogr. 33, 2608 (1977).10.1107/S0567740877009005Search in Google Scholar

[40] N. Etkin, M. T. Benson, S. S. Courtenay, M. J. McGlinchey, A. D. Bain, D. W. Stephan. Organometallics.16, 3504 (1997).10.1021/om970189wSearch in Google Scholar

[41] P. J. Chirik, J. A. Pool, E. Lobkovsky. Angew. Chem., Int. Ed.41, 3463 (2002).10.1002/1521-3773(20020916)41:18<3463::AID-ANIE3463>3.0.CO;2-PSearch in Google Scholar

[42] O. J. Scherer, M. Swarowsky, H. Swarowsky, G. Wolmersh. Angew. Chem. Int. Ed.27, 694 (1988).10.1002/anie.198806941Search in Google Scholar

[43] J. Ott, L. M. Venanzi, C. A. Ghilardi, S. Midollini, A. Orlandini. J. Organomet. Chem.291, 89 (1985).10.1016/0022-328X(85)80205-9Search in Google Scholar

[44] P. Janser, L. M. Venanzi, F. J. Bachechi. J. Organomet. Chem. 296, 229 (1985).10.1016/0022-328X(85)80351-XSearch in Google Scholar

[45] C. Bianchini, C. Mealli, A. Meli, L. Sacconi. Inorg. Chim. Acta.37, 54 (1979).10.1016/S0020-1693(00)95502-6Search in Google Scholar

[46] M. Di Vaira, P. Stoppioni, L. Sacconi. J. Organomet. Chem. 250, 183 (1983).10.1016/0022-328X(83)85049-9Search in Google Scholar

[47] M. Peruzzini, J. A. Ramirez, F. Vizza. Angew. Chem. Int. Ed. Engl. 37, 2255 (1998).10.1002/(SICI)1521-3773(19980904)37:16<2255::AID-ANIE2255>3.0.CO;2-HSearch in Google Scholar

[48] P. Barbaro, M. Peruzzini, J. A. Ramirez, F. Vizza. Organometallics. 18, 4237 (1999).10.1021/om990550+Search in Google Scholar

[49] P. Barbaro, A. Ienco, C. Mealli, M. Peruzzini, O. J. Scherer, G. Schmitt, F. Vizza, G. Wolmershäuser. Chem. Eur. J.9, 5195 (2003).10.1002/chem.200305091Search in Google Scholar PubMed

[50] M. Di Vaira, S. Seniori Costantini, P. Stoppioni, P. Frediani, M. Peruzzini. Dalton Trans. 2234 (2005).10.1039/b504795aSearch in Google Scholar PubMed

[51] M. Caporali, F. D. Calvo, C. Bazzicalupi, S. S. Costantini, M. Peruzzini. J. Organomet. Chem.859, 68 (2018).10.1016/j.jorganchem.2018.01.005Search in Google Scholar

[52] D. Akbayeva, M. Di Vaira, S. Seniori Costantini, P. Stoppioni, M. Peruzzini, Dalton Trans. 389 (2006).10.1039/B510479CSearch in Google Scholar

[53] K. X. Bhattacharyya, S. Dreyfuss, N. Saffon-Merceron, N. Mexeilles. J. Chem. Soc. Chem. Commun.52, 5179 (2016).10.1039/C6CC01683ASearch in Google Scholar PubMed

[54] V. H. Schäfer, G. Fritz, W. Hölderich. Z. Anorg. Allg. Chem. 428, 222 (1997).10.1002/zaac.19774280127Search in Google Scholar

[55] A. Wiesner, S. Steinhauer, H. Beckers, C. Müller, S. Riedel. Chem. Sci. 9, 7169 (2018).10.1039/C8SC03023ESearch in Google Scholar PubMed PubMed Central

[56] H. Lund. J. Electrochem. Soc. 149, S21 (2002).10.1149/1.1462037Search in Google Scholar

[57] J. Y. Nedelec, J. Perichon, M. Troupel. Topics in Current Chemistry, E. Steckhan (Ed.), pp. 141, Springer, Berlin-Heidelberg (1997).Search in Google Scholar

[58] J. Ludvik, D. H. Evans, D. L. Lichtenberger. Organometallics. 33, 4513 (2014).10.1021/om5008709Search in Google Scholar

[59] Z. N. Gafurov, O. G. Sinyashin, D. G. Yakhvarov. Pure Appl. Chem.89, 1089 (2017).10.1515/pac-2017-0202Search in Google Scholar

[60] D. G. Yakhvarov, E. V. Gorbachuk, O. G. Sinyashin. Eur. J. Inorg. Chem. 27, 4709 (2013).10.1002/ejic.201300845Search in Google Scholar

[61] Yu. I. Baranov, V. V. Turygin, A. Tomilov, A. V. Khudenko, I. N. Chernykh. Russ. Patent2225, 463 (2004).Search in Google Scholar

[62] A. Tomilov, A. V. Chudenko, Yu. I. Baranov, I. N. Cernyc, V. V. Turygin. Germany Patent19641, 526 (1998).Search in Google Scholar

[63] A. S. Romakhin, I. M. Zaripov, Yu. G. Budnikova, Yu. M. Kargin, E. V. Nikitin, A. Tomilov, Yu. A. Ignat’ev. Bull. Russ. Acad. Sciences Division of Chem. Science41, 1036 (1992).10.1007/BF00866580Search in Google Scholar

[64] Yu. G. Budnikova, Yu. M. Kargin, I. M. Zaripov, A. S. Romakhin, Yu. A. Ignat’ev, E. V. Nikitin, A. Tomilov, V. V. Smirnov. Bull. Russ. Acad. Sciences Division of Chem. Science41, 1580 (1992).10.1007/BF00863576Search in Google Scholar

[65] A. S. Romakhin, I. M. Zaripov, Yu. G. Budnikova, Yu. A. Ignat’ev, E. V. Nikitin, Yu. M. Kargin, A. Tomilov. Inventor’s certificate 149492, 9/09 (1987).Search in Google Scholar

[66] A. S. Romakhin, I. M. Zaripov, Yu. G. Budnikova, Yu. A. Ignat’ev, V. V. Smirnov, E. V. Nikitin, Yu. M. Kargin, A., Tomilov. Inventor’s certificate 1594951, 9/09 (1988).Search in Google Scholar

[67] A. S. Romakhin, I. M. Zaripov, Yu. G. Budnikova, Yu. A. Ignat’ev, E. V. Nikitin, Yu. M. Kargin. Electrokhimiya25, 780 (1989).Search in Google Scholar

[68] Yu. G. Budnikova, Yu. M. Kargin, O. G. Sinyashin. Phosphorus and Sulfur144/146, 555 (1999).10.1080/10426509908546307Search in Google Scholar

[69] Yu. G. Budnikova, Yu. M. Kargin, I. M. Zaripov, A. S. Romakhin, Yu. A. Ignat’ev, E. V. Nikitin, A. Tomilov. Bull. Russ. Acad. Sciences Division of Chem. Science41, 1585 (1992).10.1007/BF00863577Search in Google Scholar

[70] Yu. G. Budnikova, Yu. M. Kargin, A. S. Romakhin, O. G. Sinyashin. Russian Patent2199, 545 (2003).Search in Google Scholar

[71] Yu. G. Budnikova, D. G. Yakhvarov, O. G. Sinyashin. J. Organomet. Chem.690, 2416 (2005).10.1016/j.jorganchem.2004.11.008Search in Google Scholar

[72] Yu. H. Budnikova, S. A. Krasnov, T. V. Gryaznova, A. P. Tomilov, V. V. Turigin, I. M. Magdeev, O. G. Sinyashin, Phosphorus, Sulfur, and Silicon.183, 513 (2008).10.1080/10426500701761672Search in Google Scholar

[73] D. G. Yakhvarov, E. V. Gorbachuk, R. M. Kagirov, O. G. Sinyashin. Russ. Chem. Bull.61, 1300 (2012).10.1007/s11172-012-0176-5Search in Google Scholar

[74] D. G. Yakhvarov, Yu. G. Budnikova, O. G. Sinyashin. Russ. J. Electrochem.39, 1261 (2003).10.1023/B:RUEL.0000003456.78545.0dSearch in Google Scholar

[75] Yu. G. Budnikova, J. Perichon, D. G. Yakhvarov, Yu. M. Kargin, O. G. Sinyashin. J. Organomet. Chem.630, 185 (2001).10.1016/S0022-328X(01)00813-0Search in Google Scholar

[76] V. A. Milyukov, Yu. G. Budnikova, O. G. Sinyashin. Russ. Chem. Rev.74, 781 (2005).10.1070/RC2005v074n09ABEH001182Search in Google Scholar

[77] I. N. Brago, A. Tomilov. Electrokhimiya4, 697 (1968).Search in Google Scholar

[78] N. Ya. Shandrinov, A. Tomilov. Electrokhimiya4, 237 (1968).Search in Google Scholar

[79] I. M. Osadchenko, A. Tomilov. Zhurn. Prikl. Khimii43, 1255 (1970).Search in Google Scholar

[80] W. Behrendt, U. W. Gerwarth, R. Haubold, J. v. Jouanne, H. Keller-Rudeck, D. Koschel, H. Schäfer, J. Wagner. P Phosphorus: Mononuclear Compounds with Hydrogen. Springer-Verlag, Berlin, Heidelberg (1993). DOI: 10.1007/978-3-662-08847-0.10.1007/978-3-662-08847-0Search in Google Scholar

[81] D. Yakhvarov, M. Caporali, L. Gonsalvi, Sh. Latypov, V. Mirabello, I. Rizvanov, O. Sinyashin, P. Stoppioni, M. Peruzzini, W. Schipper. Angew. Chem. Int. Ed.50, 5370 (2011).10.1002/anie.201100822Search in Google Scholar PubMed

[82] E. V. Gorbachuk, Kh. R. Khayarov, O. G. Sinyashin, D. G. Yakhvarov. Mendeleev Commun.24, 334 (2014).10.1016/j.mencom.2014.11.005Search in Google Scholar

[83] E. V. Gorbachuk, E. K. Badeeva, V. M. Babaev, I. Kh. Rizvanov, R. G. Zinnatullin, P. O. Pavlov, Kh. R. Khayarov, D. G. Yakhvarov. Russ. Chem. Bull.65, 1289 (2016).10.1007/s11172-016-1450-8Search in Google Scholar

[84] Y. Madrid, C. Camara. Analyst.119, 1647 (1994).10.1039/AN9941901647Search in Google Scholar

Published Online: 2019-01-17
Published in Print: 2019-05-27

©2019 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/