Next Article in Journal
Dynamic Changes in Glutenin Macropolymer during Different Dough Mixing and Resting Processes
Next Article in Special Issue
Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation
Previous Article in Journal
Identification and Quantification of Polycyclic Aromatic Hydrocarbons in Polyhydroxyalkanoates Produced from Mixed Microbial Cultures and Municipal Organic Wastes at Pilot Scale
Previous Article in Special Issue
Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 26
Issue 3
10.3390/molecules26030538
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}

by
Airat M. Kuchkaev
1,2,
Nikita Y. Shmelev
1,3,4,
Aidar M. Kuchkaev
1,2,
Aleksandr V. Sukhov
1,2,
Vasily M. Babaev
1,
Khasan R. Khayarov
2,
Artem L. Gushchin
3,*,
Maxim N. Sokolov
3,4,
Oleg G. Sinyashin
1 and
Dmitry G. Yakhvarov
1,2,*
1
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of the Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, Russia
2
Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya Str. 18, 420008 Kazan, Russia
3
Nikolaev Institute of Inorganic Chemistry SB RAS Lavrentiev av. 3, 630090 Novosibirsk, Russia
4
Department of Natural Sciences, Novosibirsk State University, Pirogov Str. 2, 630090 Novosibirsk, Russia
*
Authors to whom correspondence should be addressed.
Molecules 2021, 26(3), 538; https://doi.org/10.3390/molecules26030538
Submission received: 28 December 2020 / Revised: 18 January 2021 / Accepted: 18 January 2021 / Published: 21 January 2021
(This article belongs to the Special Issue Molecular Metal Clusters: Fundamental and Applied Aspects)
Browse Figures
Review Reports Versions Notes

Abstract

:
Reaction of heterometallic cubane-type cluster complexes—[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6, where dba—dibenzylideneacetone, dbbpy—4,4′-di-tert-butyl-2,2′-bipyridine, tu—thiourea, acac—acetylacetonate, py—pyridine, with white phosphorus (P4) in the presence of water leads to the formation of phosphorous acid H3PO3 as the major product. The crucial role of the Pd atom in the cluster core {Mo3PdS4} has been established in the hydrolytic activation of P4 molecule. The main intermediate of the process, the cluster complex [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ with coordinated P(OH)3 molecule and phosphine PH3, have been detected by 31P NMR spectroscopy in the reaction mixture.

1. Introduction

Both organic and inorganic phosphorus-containing compounds have become widespread agents for various industrial applications. Traditional methods for the preparation of phosphorus compounds involve oxidation and chlorination of the element (white) phosphorus (P4) and use the phosphorus chlorides as phosphorylating agents for the synthesis of various organophosphorus substrates. It should be noted that direct activation and transformation of P4 is a very harsh and risky process that involves toxic and hazardous reagents and waste, and which negatively impacts on the environment.
The oxidation of P4 in the presence of H2O usually leads to the formation of phosphoric acid H3PO4, while phosphorous acid H3PO3 is more interesting and important phosphorus precursor which can be used as a phosphorylating agent as it contains a functionally capable P-H bond. Moreover, the current methods for the preparation of H3PO3 leave much to desire and require the use of toxic and hazardous phosphorus trichloride producing a huge amount of corrosive gaseous hydrogen chloride and dangerous phosphorus chloro-derivatives.
We have previously demonstrated that palladium complexes can be efficiently used for the preparation of phosphorous acid H3PO3 directly from P4 by its mild hydrolysis in the coordination sphere of the metal [1,2]. However, the main limitation of these catalytic systems is the formation of catalytically inactive palladium phosphides and palladium black [3]. It is important to note, that ruthenium-mediated P4 hydrolysis was thoroughly studied in Florence in the scientific group of M. Peruzzini and P. Stoppioni. It was shown that the hydrolysis of [CpRu(PPh3)2(η1-P4)] (Cp = cyclopentadienyl) complex leads to the formation of phosphine PH3 and phosphorous acid H3PO3 [4,5]. Moreover, it has been established that the mechanism of this process may involve the formation of binuclear intermediate, when η2-P4unite is doubly coordinated to two {CpRu(PPh3)2} moieties, which is hydrolyzed with the formation of H3PO3 and previously unknown 1-hydroxytriphosphane (PH(OH)PHPH2) as the intermediate of the overall process [6]. Later this process was improved and the kinetic of P4 hydrolysis was investigated using ruthenium complexes with water-soluble phosphine ligands [7]. There is also a notable example of stabilization of phosphorous acid H3PO3 in its tautomeric form P(OH)3 on the Ru site [8]. Hence, further development of new methods of white phosphorus hydrolysis is of high interest.
Heterometallic cubane-type cluster complexes with {M3PdS4} (M = Mo, W) core that were first described by Hidai’s group in Japan [9,10], possess a number of attractive properties including unordinary reactivity and catalytic activity of the Pd site [11,12,13,14,15,16,17,18,19,20,21,22]. To cite the most recent example, {Mo3PdS4} cluster complexes react with fullerene C60 to form hybrid compounds containing a fullerene molecule coordinated to palladium in the cluster core [23]. The {M3PdS4} clusters catalyze allylation of aromatics [24,25,26] and nucleophilic addition to triple bonds [10,27]. However, until now there have been no examples of P4 molecule coordination and activation in the coordination sphere of the {Mo3PdS4} cluster core, despite reported ability of such clusters to stabilize the unstable species or less-favoured tautomers, such as As(OH)3, P(OH)3, PhP(OH)2, Ph2P(OH), HP(OH)2 through coordination to the palladium site, which indicates high affinity of the latter for pnictogens. [28,29]. From these earlier studies, we have assumed that {Mo3PdS4} complexes could be involved in the process of P4 activation and its transformation.
In this work we investigated the reactivity of heterometallic complexes [Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6(1), [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl (2) and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6 (3) towards element (white) phosphorus.

2. Results and Discussion

2.1. Synthesis and Characterization

The trinuclear cluster complexes with the {M3S4} (M = Mo, W) core are able to incorporate a range of transition metals in low oxidation state (from 0 to +2), affording heterometallic cubane-type derivatives {M3M′S4}, where M′ = Cu, Ni, Pd, Pt, etc. [11,30,31,32,33,34,35].
The common approach for synthesis of the {M3M’S4} clusters involves the reaction of a low-valent metal precursor with a {M3S4} trinuclear complex in a desired coordination environment [12]. The same synthetic approach has been applied in current work, where [Pd2(dba)3] × CHCl3 was used as the palladium source. The synthetic routes to new cluster complexes 1 and 3 used in this work are depicted in Scheme 1. The cluster complex 2 has been obtained according to a previously published procedure [36].
The reaction of [Mo3S4Cl3(dbbpy)3]PF6 with [Pd2(dba)3] × CHCl3 (2:1 molar ratio) in CH2Cl2 gives complex 1 in 54% yield. The complex 3 was prepared in a similar way in 47% yield from [Mo3S4(acac)3(py)3]PF6 as starting compound. The formation and identity of 1 and 3 were confirmed by microanalysis and spectroscopic data.
The IR spectrum of 1 demonstrates the characteristic composite vibration bands, ν(C–C) and ν(C–N) at 1610 cm–1; ν(C-C), δ(C-H), δ(C-N) and δ(Mo-N) in the 1480–1410 cm−1 range; γ(C-H) and δ(C-H) in the 870–830 cm−1 and 1380–1310 cm−1 regions, and ring breathing bands from the coordinated dbbpy ligands in the 1028–906 and 766–423 cm–1 regions. The spectral data are in agreement with those reported for complex 2 [36]. The intensive band (ν(C=O)) at 1625 cm−1 testifies the coordination of dba ligand to the palladium atom, while bands at 839 and 555 cm−1 belong to the hexafluorophosphate anion.
In the case of 3, the IR spectrum is complicated by a significant overlap between bands from acac and py ligands. The band at 1603 cm−1 (ν(C=C + C-N)) relates to the bonded pyridine, and the two characteristic bands (ν(C=C + C=O)) at 1578 and 1523 cm−1 are associated with the acetylacetonate ligand. The two intensive bands at 838 and 556 cm−1 are explained by the presence of PF6− group. The highly intensive band at 1627 cm−1 reveals the presence of coordinated dba [37].
The 1H NMR spectra of both 1 and 3 in CDCl3 demonstrate a complicated pattern due to the presence of overlapping signals in the 7–9 ppm area, that originate from the protons of various aromatic rings present in dbbpy, py, and dba ligands. There are also signals related to alkene fragments in dba (δ ~ 7 ppm). The characteristic signals generated by protons of the tert-butyl group (δ 1.40–1.45 ppm) in dbbpy ligand are detected in the case of 1. The spectrum of 3 contains peaks associated with CH3- (δ 1.85 ppm) and CH-groups (δ 5.36 ppm) in acac.
The ESI-MS (+) of 1 contains the peaks with m/z ratio = 1669 ([Mo3{Pd(dba)}S4Cl3(dbbpy)3]+) (pseudomolecular peak), 1436 ([Mo3PdS4Cl3(dbbpy)3]+), 1476 ([Mo3{Pd(CH3CN)}S4Cl3(dbbpy)3]+), 1327 ([Mo3S4Cl3(dbbpy)3]+) which result from [Mo3{Pd(dba)}S4Cl3(dbbpy)3]+ fragmentation under experimental conditions. The signals with m/z ratio of 1057.8 ([Mo3PdS4(acac)3(py)3]+), 978.6 ([Mo3PdS4(acac)3(py)2]+), 899.6 ([Mo3PdS4(acac)3(py)]+), 951.8 ([Mo3S4(acac)3(py)3]+), 870.8 ([Mo3S4(acac)3(py)2]+), 793.8 ([Mo3S4(acac)3(py)]+), 714.7 ([Mo3S4(acac)3]+) are detected in the spectrum of 3. The de-coordination of the pyridine ligands is expectable under ionization conditions and was also observed for the trinuclear {Mo3S4} precursor [38]. All the peaks have been assigned both from m/z and characteristic isotope patterns.

2.2. Interaction with P4

The reactivity of heterometallic cluster complexes [Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6 (1), [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl (2) and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6 (3) towards P4 was investigated both in the absence and in the presence of water. According to 31P NMR spectra, addition of the equimolar amount of P4 to the solutions of these complexes in DMF, THF and CH2Cl2 does not lead to transformation of P4 molecule, and no new signals from phosphorus-containing species were detected.
However, addition of water to the DMF solutions containing complexes 1 or 2 and P4 has led to the appearance of the signals associated with inorganic oxo-acids H3PO3 (δ 2.1 ppm) and H3PO4 (δ 0.9 ppm) with integral ratio of 3.4:1.0 (for 1) and 7.5:1.0 (for 2). Additionally, new signals around 110 ppm were detected. These signals correspond to the formation of [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ (Figure 1), in which the Pd atoms bears the tautomeric form of phosphorous acid H3PO3 (P(OH)3) formed by the hydrolysis of white phosphorus. These results nicely fit with the previously published data [28,29], where the signals around 115 ppm in 31P NMR spectra were attributed to the complexes [Mo3{PdP(OH)3}S4(H2O)9-xClx](4–x)+ obtained by the reaction of [Mo3{PdCl}S4(H2O)9]3+ with PCl3 or H3PO3 in 4M HCl. The total conversion of white phosphorus (by 31P NMR spectroscopy) in these reactions was 96.7% for complex 1 and 68.0% for complex 2.
In order to boost the activity of clusters 1 and 2, we attempted modification of their ligand surrounding by the substitution of the chloride-ions from the first and the second coordination spheres with weakly coordinated ions, and in this way to increase the electrophilic properties of Pd. Indeed, addition of TlNO3 as a halide scavenger increased the reactivity of the cluster towards P4. As a result, increased intensity of the signals related to H3PO3 and H3PO4, and the decreased intensity of the P4 signal were observed in 31P NMR spectra. In the case of complex 1, full conversion of P4 was accomplished with a 72.0% yield of H3PO3. Complex 2 gave 74.4% conversion of P4 and 53.1% yield of H3PO3.
Addition of H2O to the reaction mixture containing [Mo3{Pd(dba)}S4(acac)3(py)3]PF6 (3) in DMF and P4 also allowed for the appearance of the signals associated with H3PO3 and H3PO4. The conversion of P4 (34.4%) was, however, substantially lower than with 1 and 2 and no signal attributed to [Mo3{PdP(OH)3}S4(acac)3(py)3]+ was observed in 31P NMR spectrum. This can be explained by assuming [Mo3{PdP(OH)3}S4(acac)3(py)3]+ being less stable than [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+, and quickly releases P(OH)3, which tautomerizes into the final product—phosphorous acid. The observed yield of H3PO3 was only 20.1%.
The solvent influence on the reactivity of P4 and its hydrolysis was also investigated, using the complex 1 as the benchmark. Addition of an excess of H2O to the reaction mixture containing 1 and P4 in CH2Cl2 allowed for detection of the signals associated with [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ (δ 110 ppm), H3PO3 (δ 4.7 ppm) and H3PO4 (δ 1.1 ppm). Adding TlNO3 increased the signal intensities, and the observed molar ratio of H3PO3:H3PO4 was 3:2. The signal at δ −243.6 ppm related to the formation of PH3 was also observed, as minor peak. The conversion of P4 was 43.1% with only 8.6% yield of H3PO3.
In case of THF as the solvent, the addition of H2O to the reaction mixture containing 1 and P4 yielded the signal associated with [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ with δ +113.8 ppm in 31P NMR spectrum. It is worth noting that there were no signals of any phosphorus-containing acids in 31P NMR spectra in this case. However, the activation of the complex with TlNO3 caused both the signal growth and the appearance of new signals related to H3PO3 (δ 3.3 ppm), H3PO4 (δ 1.1 ppm), and PH3 (δ −244.4 ppm). The integrated intensity ratio H3PO3:H3PO4 was 8:3, and the observed conversion of P4 was 85.5% with 24.4% yield of H3PO3.
The summary of the results obtained in the reaction of {Mo3PdS4} complexes with P4 is presented in Table 1.
It should be noted, that the presence of the Pd site in the cluster moiety to realise the hydrolysis of P4 molecule is mandatory, as this reaction does not proceed with Pd-free trinuclear cluster complexes [Mo3S4Cl3(dbbpy)3]Cl and [Mo3S4Cl3(dbbpy)3]PF6. This fact confirms that the transformation and followed hydrolysis of P4 requires the presence of Pd center. Moreover, the use of cluster core {Mo3PdS4} for hydrolysis of white phosphorus tetrahedron and its transformation into phosphorous acid (H3PO3) allows to avoid the formation of the insoluble and inactive Pd-black that is very important for the further use of these {Mo3PdS4} clusters as catalysts for the hydrolysis of white phosphorus.

3. Conclusions

Based on the experimental data, we can conclude that heterometallic cubane-type clusters [Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6 (1), [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl (2) and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6 (3) efficiently promote the hydrolysis of P4 molecule leading to the formation of H3PO3 as the major product. The complexes 1 and 2 bearing dbbpy ligand demonstrate higher activity in comparison with complex 3 containing acac ligand. Moreover, removal chloride anions from the coordination sphere of the cluster core with TlNO3 increases both the activity of the cluster complexes in P4 activation process and the yield of H3PO3. The use of the cluster with embedded Pd atom allows to avoid the Pd black formation which occurs when non-cluster Pd complexes are used for white phosphorus hydrolysis process. Thus, this work opens up prospects for studying the potential of heterometallic cubane-type clusters as catalysts for the selective conversion of white phosphorus to phosphorous acid. Further studies are in progress.

4. Experimental Section

CAUTION: White phosphorus and phosphine mentioned in this communication are hazardous compounds. White phosphorus needs to be stored under water in a well-ventilated dark place. White phosphorus is highly toxic and burns spontaneously when exposed to air. In an emergency, white phosphorus can be treated with aqueous copper(II) sulfate solution or sand. On contact with skin, white phosphorus gives highly painful, badly healing burns. In case of skin burns, washing with diluted aqueous solutions of KMnO4 or CuSO4 is advised. The continuous inhaling of white phosphorus vapors results in disease of the bone tissue, loss of teeth, and necrosis of parts of the jaw. An aqueous copper(II) sulfate solution (2%) can be used as an immediate antidote for poisoning. All reactions and handling of phosphine and white phosphorus must be carried out under an inert atmosphere in a well-ventilated hood.
All experiments related to the synthesis of the complexes, preparation of the solutions, solvents, and the manipulations with white phosphorus and all chemical reagents were performed under nitrogen atmosphere using standard Schlenk-line techniques.
Trinuclear precursors [Mo3S4Cl3(dbbpy)3]X (X = Cl−, PF6−; dbbpy—4,4′-di-tert-Bu-2,2′-bipyridine) [39] and [Mo3S4(acac)3(py)3]PF6 (acac—acetylacetonate, py—pyridine) [40] used to synthesize complexes 1, 2 and 3 as well as complex [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl (2) (tu—thiourea) [36], were prepared according to the published procedures. Commercially available reagents [Pd2(dba)3] × CHCl3 (dba—dibenzylideneacetone) (Sigma-Aldrich, Steiheim, Germany), thallium(I) nitrate (99.5%, ACROS Organics, Geel, Belgium) were used as purchased. White phosphorus was stored under a protective nitrogen atmosphere in a flask filled with water in a dark place and was washed sequentially in ethanol, acetone, and diethyl ether prior to use. 0.05 M THF solution was prepared by dissolving P4 in a required amount of solvent. Organic solvents were distilled before used.
Elemental C, H, N analyses were performed with a EuroEA3000 Eurovector analyzer (Eurovector SpA, Milano, Italy). IR spectraof samples in KBr pellets were recorded in the 4000–400 cm−1 range with a Perkin-Elmer System 2000 FTIR spectrometer(PerkinElmer, Waltham, Massachusetts, USA). 1H and 31P{1H} NMR spectra were registered at room temperature on a Bruker Avance III 400 MHz spectrometer (Bruker, New York, New York, USA)at frequencies of 400.0 (1H) and 161.9 (31P) MHz. UV–vis spectra were recorded with a Specord M40 (Carl Zeiss, Jena, Germany), Helios γ spectrophotometer (ThermoFisher Scientific, Waltham, Massachusetts, USA) in the 200–900 nm range in the CH3CN solution. A mass spectrometer (Agilent, 6130 Quadrupole MS, 1260 infinity LC, Santa Clara, California, USA) was utilized for the ESI measurements of 1. The drying gas was nitrogen at a 300 L × h−1 flow rate. The sample solution (approx. 5 × 10−5 M) in acetonitrile was infused through a syringe pump directly into the interface at a flow rate of 0.4 mL min−1. The temperature of the source block was set to 120 °C and the interface to 150 °C. A capillary voltage of 2.0 kV was used in the positive scan mode, and low values of the cone voltage (Uc = 5–10 V) were used to control the extent of fragmentation. The observed isotopic pattern of each compound perfectly matched the theoretical isotope pattern calculated from their elemental composition by using the MassLynx 4.1 program (Waters Corporation, Milford, Massachusetts, USA). ESI measurements of 3 were performed using an AmazonX (Bruker Daltonics, Bremen, Germany) ion trap mass spectrometer in positive mode in the mass range of 200–3000 Da. The sample solution (approx. 5 × 10−5 M) in DMF was infused through a syringe pump directly into the interface at a flow rate of 0.2 mL × min−1. The ESI-MS conditions were as follows: capillary voltage, 2.5 kV; nitrogen drying gas, 10 L × min−1, 250 °C. Data processing was performed by DataAnalysis software (Bruker Daltonik GmbH, Version 4.0 SP4, Bremen, Germany).
Synthesis of [Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6 (1). A mixture of [Mo3S4Cl3(dbbpy)3]PF6 (0.2 g, 0.13 mmol) and [Pd2(dba)3] × CHCl3 (0.070 g, 0.068 mmol) was stirred in CH2Cl2 (20 mL) for 24 h. An excess of n-hexane was layered onto the resulting brown solution to give a brown product of 1 that was washed by n-hexane and diethyl ether. Yield: 0.133 g (54%).
IR (ν, cm−1): 3395 w, 3158 m, 3123 m, 2960 s, 2903 s, 2869 s, 1626 s 1618 s, 1549 m, 1477 m, 1464 m, 1415 s, 1311 w, 1295 w, 1254 m, 1201 w, 1158 w, 1129 w, 1020 m, 985 s, 975 w, 903 m, 885 w, 859 s, 830 m, 741 w, 720 w, 604 w, 555 s, 485 w, 427 w.
NMR 1H (400 MHz, CDCl3, 293 K): δ = 9.93 (d, 3H), 9.06 (3H), 8.49 (d, 3H), 8.31 (d, 3H), 7.80 (2H, dba), 7.28–7.65 (10H, dba), 7.31–7.39 (m, 6H, dbbpy), 7.01 (2H, dba), 1.45 (s, 27H, tBu), 1.40 (s, 27H, tBu) ppm.
ESI-MSI (+, CH3CN): m/z = 1671 ([Mo3{Pd(dba)}S4Cl3(dbbpy)3]+), 1437 ([Mo3PdS4Cl3(dbbpy)3]+), 1331 ([Mo3S4Cl3(dbbpy)3]+), 1313 ([Mo3S4Cl2(OH)(dbbpy)3]+), 1383 ([Mo3PdS4(OH)3(dbbpy)3]+), 1460 ([Mo3{Pd(CH3CN)}S4Cl2(OH)(dbbpy)3]+), 1277 ([Mo3S4(OH)3(dbbpy)3]+).
Anal. Calc. for C71H86Cl3F6Mo3N6OPPdS4: C, 47.0; H, 4.8; N, 4.6%. Found: C, 46.7; H, 4.4; N, 5.0%.
Synthesis of [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl (2).A mixture of [Mo3S4Cl3(dbbpy)3]Cl (0.1 g, 0.74 mmol), [Pd2(dba)3] × CHCl3 (0.038 g, 0.37 mmol), and thiourea (0.056 g, 0.74 mmol) in 20 mL of CH2Cl2 was stirred for 24 h. An excess of hexane was layered onto the resulting brown solution to give a greenish-brown product of 2. Yield: 0.080 g (71%). The obtained analytical data nicely fit with previously published results [36].
Synthesis of [Mo3{Pd(dba)}S4(acac)3(py)3]PF6 (3). A mixture of [Mo3S4(acac)3(py)3]PF6 (0.2 g, 0.17 mmol) and [Pd2(dba)3] × CHCl3 (0.089 g, 0.086 mmol) were stirred in CH2Cl2 (20 mL) for 24 h. An excess of n-hexane was layered onto the resulting brown solution to give a green-brown product of 3 that was washed by n-hexane and diethyl ether. Yield: 0.121 g (47%).
IR (ν, cm−1):2918 m, 1627s, 1611m, 1603 m, 1597s, 1578 m, 1568 m, 1523 s, 1485 m, 1444 s, 1416 m, 1366 s, 1280 s, 1177 w, 1151 w, 1066 s, 1021 s, 1013 s, 975 w, 876 s, 838 s, 782 w, 755 s, 698 s, 672 m, 622 m, 551 s, 540 m, 490s, 425 s.
NMR 1H (400 MHz, CDCl3, 293 K): δ = 9.58, 9.47 (6H, α-py), 8.15, 8.13, 8.10 (3H, γ-py), 7.80–7.30 (2H + 10H, dba; 6H, β-py), 7.03 (2H, dba) 5.36 (γ-CH, acac), 1.85 (CH3, acac) ppm.
ESI-MSI (+, DMF): m/z = 1057.8 ([Mo3PdS4(acac)3(py)3]+), 978.6 ([Mo3PdS4(acac)3(py)2]+), 899.6 ([Mo3PdS4(acac)3(py)]+), 951.8 ([Mo3S4(acac)3(py)3]+), 870.8 ([Mo3S4(acac)3(py)2]+), 793.8 ([Mo3S4(acac)3(py)]+), 714.7 ([Mo3S4(acac)3]+).
Anal. Calc. for C47H50F6Mo3N3O7PPdS4: C, 39.3; H, 3.5; N, 2.9%. Found: C, 39.0; H, 3.1; N, 3.3%.
Interaction of 1, 2, and 3 with P4 in the presence of H2O. A solution of P4 (0.0025 g, 0.02 mmol) in THF (0.4 mL) was added at room temperature to a solution of complex 1, 2, or 3 (0.02 mmol) in 1 mL of solvent (DMF, CH2Cl2, or THF). Then, H2O (0.043 mL, 2.4 mmol) was added dropwise to the reaction mixture. After 12 h of stirring, TlNO3 (0.021 g, 0.08 mmol) was added. An analysis of the reaction mixture was provided by 31P NMR spectroscopy after each of the consequent steps.

Author Contributions

Conceptualization, A.L.G. and D.G.Y.; methodology, A.L.G. and D.G.Y.; validation, A.L.G., M.N.S., O.G.S. and D.G.Y.; formal analysis, A.V.S., V.M.B. and K.R.K.; investigation, A.M.K. (Airat M. Kuchkaev), N.Y.S. and A.M.K. (Aidar M. Kuchkaev); data curation, A.M.K. (Airat M. Kuchkaev), N.Y.S. and A.M.K. (Aidar M. Kuchkaev); writing—original draft preparation, A.M.K. (Airat M. Kuchkaev) and N.Y.S.; writing—review and editing, A.L.G., M.N.S., O.G.S. and D.G.Y.; supervision, A.L.G. and D.G.Y.; project administration, A.L.G. and D.G.Y. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Russian Foundation for Basic Research (grant numbers 19-33-50136 and 18-33-20056) and by the Russian Government Program of Competitive Growth of Kazan Federal University (Reg. Nr. AAAA-A19-119053190012-8) and the Government assignment for FRC Kazan Scientific Center of RAS (Reg. Nr. AAAA-A18-118041760011-2)

Informed Consent Statement

Informed consent was obtained from all subjects involved in the study.

Data Availability Statement

Data sharing is not applicable to this article.

Acknowledgments

We acknowledge the financial support from the Russian Foundation for Basic Research (grants 19-33-50136 and 18-33-20056). The authors are thankful to the Russian Government Program of Competitive Growth of Kazan Federal University for performing of the NMR experiments in KFU and to the Government assignment for FRC Kazan Scientific Center of RAS for supporting this research activity dealing with the synthesis of the cluster complexes and phosphorus derivatives. The authors also gratefully acknowledge the CSF-SAC FRC KSC RAS for providing necessary facilities to carry out this work.

Conflicts of Interest

The authors declare no conflict of interest.

Sample Availability

Samples of the compounds 1–3 are available from the authors.

References

  1. Yakhvarov, D.G.; Kagirov, R.M.; Sinyashin, O.G. Method of Producing Phosphorous Acid from White Phosphorus. Russian Patent 2460687, 25 February 2011. [Google Scholar]
  2. Kagirov, R.M.; Voloshin, A.V.; Rizvanov, I.K.; Sinyashin, O.G.; Yakhvarov, D.G. Activation and transformation of white phosphorus by palladium(II) complexes. Russ. Chem. Bull. 2010, 59, 1116–1118. [Google Scholar] [CrossRef]
  3. Kagirov, R.M.; Voloshin, A.V.; Kadirov, M.K.; Nizameev, I.R.; Sinyashin, O.G.; Yakhvarov, D.G. Selective synthesis of nanosized palladium phosphides from white phosphorus. Mendeleev Commun. 2011, 21, 201–203. [Google Scholar] [CrossRef]
  4. Di Vaira, M.; Peruzzini, M.; Stoppioni, P. d6 metal systems for white phosphorus activation. Comptes Rendus Chim. 2010, 13, 935–942. [Google Scholar] [CrossRef]
  5. Di Vaira, M.; Frediani, P.; Costantini, S.S.; Peruzzini, M.; Stoppioni, P. Easy hydrolysis of white phosphorus coordinated to ruthenium. Dalton Trans. 2005, 2234–2236. [Google Scholar] [CrossRef] [PubMed]
  6. Barbaro, P.; Di Vaira, M.; Peruzzini, M.; Seniori Costantini, S.; Stoppioni, P. Controlling the activation of white phosphorus: Formation of phosphorous acid and ruthenium-coordinated 1-hydroxytriphosphane by hydrolysis of doubly metalated P4. Angew. Chem. Int. Ed. 2008, 47, 4425–4427. [Google Scholar] [CrossRef]
  7. Caporali, M.; Gonsalvi, L.; Kagirov, R.; Mirabello, V.; Peruzzini, M.; Sinyashin, O.; Stoppioni, P.; Yakhvarov, D. The first water-soluble tetraphosphorus ruthenium complex. Synthesis, characterization and kinetic study of its hydrolysis. J. Organomet. Chem. 2012, 714, 67–73. [Google Scholar] [CrossRef]
  8. Akbayeva, D.N.; Di Vaira, M.; Seniori Costantini, S.; Peruzzini, M.; Stoppioni, P. Stabilization of the tautomers HP(OH)2 and P(OH)3 of hypophosphorous and phosphorous acids as ligands. Dalton Trans. 2006, 389–395. [Google Scholar] [CrossRef]
  9. Murata, T.; Gao, H.; Mizobe, Y.; Nakano, F.; Motomura, S.; Tanase, T.; Yano, S.; Hidai, M. Synthesis of Mixed-Metal Sulfido Clusters with a Cuboidal Mo3PdS4 Core Which Coordinate Alkene to the Unique Palladium Site Surrounded by Sulfido Ligands. J. Am. Chem. Soc. 1992, 114, 8287–8288. [Google Scholar] [CrossRef]
  10. Murata, T.; Mizobe, Y.; Gao, H.; Ishii, Y.; Wakabayashi, T.; Nakano, F.; Hidai, M.; Echizen, I.; Nanikawa, H.; Motomura1, S.; et al. Syntheses of Mixed-Metal Sulfide Cubane-Type Clusters with the Novel PdMo3S4 Core and Reactivities of the Unique Tetrahedral Pd Site Surrounded by Sulfide Ligands toward Alkenes, CO, tBuNC, and Alkynes. J. Am. Chem. Soc. 1994, 116, 3389–3398. [Google Scholar] [CrossRef]
  11. Gushchin, A.L.; Laricheva, Y.A.; Sokolov, M.N.; Llusar, R. Tri- and tetranuclear molybdenum and tungsten chalcogenide clusters: On the way to new materials and catalysts. Russ. Chem. Rev. 2018, 87, 670–706. [Google Scholar] [CrossRef]
  12. Sokolov, M.N.; Fedin, V.P.; Sykes, A.G. Comprehensive Coordination Chemistry II; McCleverty, J.A., Meyer, T.J., Eds.; Elsevier Ltd.: Amsterdam, The Netherlands, 2004; Volume 4, pp. 761–823. [Google Scholar]
  13. Herbst, K.; Zanello, P.; Corsini, M.; D’Amelio, N.; Dahlenburg, L.; Brorson, M. A complete family of isostructural cluster compounds with cubane-like M3S4M′ cores (M = Mo, W; M′ = Ni, Pd, Pt): Comparative crystallography and electrochemistry. Inorg. Chem. 2003, 42, 974–981. [Google Scholar] [CrossRef] [PubMed]
  14. Hernandez-molina, R.; Sokolov, M.N.; Sykes, A.G. Behavioral Patterns of Heterometallic Cuboidal Derivatives of [M3Q4(H2O)9]4+ (M = Mo, W; Q = S, Se). Acc. Chem. Res. 2001, 34, 223–230. [Google Scholar] [CrossRef] [PubMed]
  15. Seino, H.; Hidai, M. Catalytic functions of cubane-type M4S4 clusters. Chem. Sci. 2011, 2, 847–857. [Google Scholar] [CrossRef]
  16. Algarra, A.G.; Fernández-Trujillo, M.J.; Safont, V.S.; Hernández-Molina, R.; Basallote, M.G. Combined kinetic and DFT studies on the stabilization of the pyramidal form of H3PO2 at the heterometal site of [Mo3M′S4(H2O)10]4+ clusters (M′ = Pd, Ni). Dalton Trans. 2009, 4, 1579–1586. [Google Scholar] [CrossRef]
  17. Kryuchkova, N.A.; Ryzhikov, M.R.; Syrokvashin, M.M. Interatomic Interactions in Heterometallic Cubane-Type Clusters with {Mo3S4M′} (M′ = Cu, Ni, Pd) Core. J. Clust. Sci. 2020. [Google Scholar] [CrossRef]
  18. Herbst, K.; Monari, M.; Brorson, M. Molecular metal sulfide cluster model for substrate binding to oil-refinery hydrodesulfurization catalysts. Inorg. Chem. 2002, 41, 1336–1338. [Google Scholar] [CrossRef]
  19. Shibahara, T. Syntheses of sulphur-bridged molybdenum and tungsten coordination compounds. Coord. Chem. Rev. 1993, 123, 73–147. [Google Scholar] [CrossRef]
  20. Hidai, M.; Kuwata, S.; Mizobe, Y. Synthesis and reactivities of cubane-type sulfido clusters containing noble metals. Acc. Chem. Res. 2000, 33, 46–52. [Google Scholar] [CrossRef]
  21. Llusar, R.; Vicent, C. Trinuclear Molybdenum and Tungsten Cluster Chalcogenides: From Solid State to Molecular Materials. Inorg. Chem. Focus III 2006, 105–120. [Google Scholar] [CrossRef]
  22. Algarra, A.G.; Feliz, M.; Fernández-Trajillo, M.J.; Llusar, R.; Safont, V.S.; Vicent, C.; Basallote, M.G. Unprecedented Solvent-assisted reactivity of hydrido W3CuS4 cubane clusters: The Non-innocent behaviour of the Cluster-core unit. Chem. A Eur. J. 2009, 15, 4582–4594. [Google Scholar] [CrossRef]
  23. Laricheva, Y.A.; Shmelev, N.Y.; Gushchin, A.L.; Sokolov, M.N. The study of the interaction of fullerene C60 with palladium-containing molybdenum clusters {CS4} by spectroscopic and calculation methods. Russ. J. Coord. Chem. 2021, in press. [Google Scholar]
  24. Tao, Y.; Wang, B.; Zhao, J.; Song, Y.; Qu, L.; Qu, J. Friedel-crafts-type allylation of nitrogen-containing aromatic compounds with allylic alcohols catalyzed by a [Mo3S4Pd(η 3-allyl)] cluster. J. Org. Chem. 2012, 77, 2942–2946. [Google Scholar] [CrossRef] [PubMed]
  25. Tao, Y.; Wang, B.; Wang, B.; Qu, L.; Qu, J. Highly efficient and regioselective allylation with allylic alcohols catalyzed by [Mo3S4Pd(η3-allyl)] clusters. Org. Lett. 2010, 12, 2726–2729. [Google Scholar] [CrossRef] [PubMed]
  26. Tao, Y.; Zhou, Y.; Qu, J.; Hidai, M. Highly efficient and regioselective allylic amination of allylic alcohols catalyzed by [Mo3PdS4] cluster. Tetrahedron Lett. 2010, 51, 1982–1984. [Google Scholar] [CrossRef]
  27. Wakabayashi, T.; Ishii, Y.; Ishikawa, K.; Hidai, M. A Novel Catalyst with a Cuboidal PdMo3S4 Core for the Cyclization of Alkynoic Acids to Enol Lactones. Angew. Chem. 1996, 35, 2123–2124. [Google Scholar] [CrossRef]
  28. Sokolov, M.N.; Virovets, A.V.; Dybtsev, D.N.; Chubarova, E.V.; Fedin, V.P.; Fenske, D. Phosphorous acid and arsenious acid as ligands. Inorg. Chem. 2001, 40, 4816–4817. [Google Scholar] [CrossRef]
  29. Sokolov, M.N.; Chubarova, E.V.; Virovets, A.V.; Llusar, R.; Fedin, V.P. Reactivity of Mo3PdS44+ cluster: Evidence for new ligands PhP(OH)2 and Ph2P(OH) and structural characterization of [Mo3(Pd(PPh3))S4(H2O)5Cl4]·0.5CH3OH·3H2O. J. Clust. Sci. 2003, 14, 227–235. [Google Scholar] [CrossRef]
  30. Oriwaki, K.M.; Oshida, R.Y.; Kashi, H.A. X-ray Structure Analysis Online Synthesis and Crystal Structure of a Sulfur-bridged Incomplete Cubane-type Molybdenum Cluster with a Tris(pyrazolyl)methanesulfonate Ligand. X-ray Struct. Anal. Online 2014, 30, 11–12. [Google Scholar] [CrossRef] [Green Version]
  31. Ohki, Y.; Hara, R.; Munakata, K.; Tada, M.; Takayama, T.; Sakai, Y.; Cramer, R.E. Synthesis of [Mo3S4] Clusters from Half-Sandwich Molybdenum(V) Chlorides and Their Application as Platforms for [Mo3S4Fe] Cubes. Inorg. Chem. 2019, 58, 5230–5240. [Google Scholar] [CrossRef]
  32. Pedrajas, E.; Sorribes, I.; Guillamón, E.; Junge, K.; Beller, M.; Llusar, R. Efficient and Selective N-Methylation of Nitroarenes under Mild Reaction Conditions. Chem. A Eur. J. 2017, 23, 13205–13212. [Google Scholar] [CrossRef]
  33. Ohki, Y.; Uchida, K.; Hara, R.; Kachi, M.; Fujisawa, M.; Tada, M.; Sakai, Y.; Sameera, W.M.C. Cubane-Type [Mo3S4M] Clusters with First-Row Groups 4–10 Transition-Metal Halides Supported by C5Me5 Ligands on Molybdenum. Chem. A Eur. J. 2018, 24, 17138–17147. [Google Scholar] [CrossRef] [PubMed]
  34. Petrov, P.A.; Sukhikh, T.S. Phosphine-substituted Cubane Clusters with the Mo3S4Ga Core. Russ. J. Coord. Chem. 2019, 45, 333–339. [Google Scholar] [CrossRef]
  35. Gushchin, A.L.; Sokolov, M.N.; Naumov, D.Y.; Fedin, V.P. Crystal structure of K2[Mo3(PdPPh3)S4(C2O4)3(H2O)3]·0.5H2O. J. Struct. Chem. 2008, 49, 748–752. [Google Scholar] [CrossRef]
  36. Laricheva, Y.A.; Gushchin, A.L.; Abramov, P.A.; Sokolov, M.N. Novel mixed-metal cubane-type {Mo3NiS4} and {Mo3PdS4} clusters coordinated with 2,2′-bipyridine type ligands. Polyhedron 2018, 154, 202–208. [Google Scholar] [CrossRef]
  37. Algarra, G.; Gushchin, A.L.; Abramov, P.A.; Bustelo, E.; Llusar, R. Kinetics Aspects of the Reversible Assembly of Copper in Heterometallic Mo3CuS4 Clusters with 4,4′-Di-tert-butyl-2,2′-bipyridine. Inorg. Chem. 2016, 55, 9912–9922. [Google Scholar] [CrossRef]
  38. Ukai, T.; Kawazura, H.; Ishii, Y.; Bonnet, J.J.; Ibers, J.A. Chemistry of dibenzylideneacetone-palladium(0) complexes. Novel tris(dibenzylideneacetone)dipalladium(solvent) complexes and their reactions with quinones. J. Organomet. Chem. 1974, 65, 253–266. [Google Scholar] [CrossRef]
  39. Pino-Chamorro, J.A.; Laricheva, Y.A.; Guillamón, E.; Fernández-Trujillo, M.J.; Bustelo, E.; Gushchin, A.L.; Shmelev, N.Y.; Abramov, P.A.; Sokolov, M.N.; Llusar, R.; et al. Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: A combined experimental and theoretical approach. New J. Chem. 2016, 40, 7872–7880. [Google Scholar] [CrossRef] [Green Version]
  40. Hernández-Molina, R.; Sokolov, M.; Clegg, W.; Esparza, P.; Mederos, A. Preparation and characterization of triangular clusters [M3Q4(acac)3(py)3]+ (M = Mo, W; Q = S, Se). Inorganica Chim. Acta 2002, 331, 52–58. [Google Scholar] [CrossRef]
Molecules 26 00538 sch001 550
Scheme 1. Synthesis of cubane-type cluster complexes 1 and 3.
Scheme 1. Synthesis of cubane-type cluster complexes 1 and 3.
Molecules 26 00538 sch001
Molecules 26 00538 g001 550
Figure 1. Structure of [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+.
Figure 1. Structure of [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+.
Molecules 26 00538 g001
Table
Table 1. Interaction of {Mo3PdS4} complexes 1–3 with P4.
Table 1. Interaction of {Mo3PdS4} complexes 1–3 with P4.
Complex.SolventComplex + P4 + H2OComplex + P4 + H2O + TlNO3
Conversion of P4 (%)Yield of H3PO3 (%)/H3PO4 (%)Conversion of P4 (%)Yield of H3PO3 (%)/H3PO4 (%)
1DMF96.761.5/20.5100.072.0/27.9
CH2Cl233.66.1/1.243.18.6/4.3
THF140/085.524.4/10.4
2DMF68.837.1/3.774.453.1/16.2
3DMF34.420.1/11.6--
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Kuchkaev, A.M.; Shmelev, N.Y.; Kuchkaev, A.M.; Sukhov, A.V.; Babaev, V.M.; Khayarov, K.R.; Gushchin, A.L.; Sokolov, M.N.; Sinyashin, O.G.; Yakhvarov, D.G. Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}. Molecules 2021, 26, 538. https://doi.org/10.3390/molecules26030538

AMA Style

Kuchkaev AM, Shmelev NY, Kuchkaev AM, Sukhov AV, Babaev VM, Khayarov KR, Gushchin AL, Sokolov MN, Sinyashin OG, Yakhvarov DG. Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}. Molecules. 2021; 26(3):538. https://doi.org/10.3390/molecules26030538

Chicago/Turabian Style

Kuchkaev, Airat M., Nikita Y. Shmelev, Aidar M. Kuchkaev, Aleksandr V. Sukhov, Vasily M. Babaev, Khasan R. Khayarov, Artem L. Gushchin, Maxim N. Sokolov, Oleg G. Sinyashin, and Dmitry G. Yakhvarov. 2021. "Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}" Molecules 26, no. 3: 538. https://doi.org/10.3390/molecules26030538

APA Style

Kuchkaev, A. M., Shmelev, N. Y., Kuchkaev, A. M., Sukhov, A. V., Babaev, V. M., Khayarov, K. R., Gushchin, A. L., Sokolov, M. N., Sinyashin, O. G., & Yakhvarov, D. G. (2021). Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}. Molecules, 26(3), 538. https://doi.org/10.3390/molecules26030538

Article Metrics

Back to TopTop