Next Article in Journal
3-[4-(2-Phenylethyl)piperazin-1-yl]-7H-benzo[de]anthracen-7-one
Next Article in Special Issue
Diethyl 2-((aryl(alkyl)amino)methylene)malonates: Unreported Mycelial Growth Inhibitors against Fusarium oxysporum
Previous Article in Journal
[6-(Thiophen-2-yl)-2,2′-bipyridine]bis(triphenylphosphine) Copper(I) Tetrafluoroborate
Previous Article in Special Issue
(Z)-2′-((Adamantan-1-yl)thio)-1,1′-dimethyl-2′,3′-dihydro-[2,4′-biimidazolylidene]-4,5,5′(1H,1′H,3H)-trione
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Communication

Manganese(II) Bromide Coordination toward the Target Product and By-Product of the Condensation Reaction between 2-Picolylamine and Acenaphthenequinone

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Street, Kazan 420088, Russia
*
Author to whom correspondence should be addressed.
Molbank 2023, 2023(1), M1606; https://doi.org/10.3390/M1606
Submission received: 27 February 2023 / Revised: 20 March 2023 / Accepted: 20 March 2023 / Published: 22 March 2023
(This article belongs to the Collection Molecules from Side Reactions)

Abstract

:
A heteroleptic binuclear manganese complex was obtained and characterized by single-crystal X-ray diffraction. Manganese ions coordinate with the target product and by-product of the condensation reaction between 2-picolylamine and acenaphthenequinone are characterized by different geometries in the resulting complex.

1. Introduction

Transition metal complexes with bis-iminoacenaphthenes (BIANs) are found in application in different areas of modern chemistry [1]; for instance, they serve as catalysts for many types of organic reactions [2,3,4,5,6] and act as magnetoactive [7,8] and optical [9] materials. Manganese complexes are of special interest because of their potential activity in small molecule activation [10].
The synthesis of alkyl-BIANs is often complicated by side reactions occurring between alkyl-substituted primary amines and acenaphthenequinone (AQ) [11,12,13,14,15,16]. This is the reason for a limited number of known, well-characterized alkyl-BIANs. Sometimes, the reaction of primary alkyl amine with AQ leads to a large number of by-products, whereas the desired product is practically absent. For example, as a result of the reaction of AQ with benzylamine, the authors identified several by-products, as shown in Scheme 1 [11,12,13,14,15,16]. This behavior can be explained by a set of isomerization/tautomerization, oxidation, and hydrolysis reactions during the treatment of primary aliphatic amine and AQ.

2. Results

In this work, we performed an in situ condensation reaction between 2-picolylamine and AQ. Our efforts to purify the reaction mixture by column chromatography failed because of air sensitivity and the formation of an insoluble resinous precipitate. Therefore, we carried out an in situ chemical reduction of the crude reaction mixture obtained in the previous step by metallic sodium (1.1 equiv. per 1 mol of initial AQ) in an inert nitrogen atmosphere. After sodium was fully dissolved, manganese(II) bromide was added. The resulting product was crystallized to give manganese complex 1. Isolated complex 1 demonstrated EPR silence at room temperature. The 1H NMR spectrum of complex 1 was also not informative because of the broadening of proton signals (see Supplementary Materials). We managed to describe the molecular structure of 1 by single-crystal X-ray diffraction. Thus, it was found that neutral binuclear complex 1 contained not only the target mono-iminoacenaphthene ligand (L1) but also an unexpected 14-(pyridin-2-yl)-14H-acenaphtho[1,2-b]naphtho[1,8-fg]quinoxalin-14-ol ligand (L2). The overall reaction scheme and structural formula of the final product are shown in Scheme 2.
Complex 1 crystallized in the triclinic space group P 1 ¯ with tetrahydrofuran (THF) solvent molecules. According to X-ray diffraction data, compound 1 was a neutral binuclear complex with the Mn1···Mn2 internuclear distance of 3.2818(7) Å, indicating the absence of metal–metal bonding, as shown in Figure 1. The manganese atoms differed in their coordination geometry, namely, the atom Mn1 adopted distorted square pyramidal coordination with geometry index [17] τ 5 = 0.19, while the atom Mn2 was close to octahedral one if the elongated coordination bond Mn2–N3 of 2.493(3) Å was taken into account. The ligand L1 was coordinated by Mn1 via the atoms O1, N1, and N2, whereas the ligand L2 bound Mn2 through the atoms N3, N5, and O2 as well as Mn1 through the oxygen atom O2. Internuclear distances of the coordination sphere are listed in the figure caption. The positions of the hydrogen atoms of 1 were confirmed by Fourier maps and corresponded to the skeletal formula in Scheme 2. The analysis of bond lengths within the ligand L1 in complex 1 showed the migration of double bond from N1–C102 (1.369(5) Å) to N1–C21 (1.289(5) Å). The charge distribution analysis showed that L2 was an anion with a formal negative charge of −1 on oxygen atom O2. The ligand L1 also demonstrated anionic character.

3. Materials and Methods

Preparation. All manipulations were carried out under nitrogen, using the standard Schlenk technique or in a glove box. The solvents (THF and hexane) were distilled from sodium/benzophenone and stored over 3 Å molecular sieves under nitrogen gas. Acenaphthenequinone (95%, CAS—82-86-0), 2-aminomethyl-pyridine (99%, CAS 3731-51-9), and manganese(II) bromide MnBr2 (98%, CAS 13446-03-2) were purchased and used without preliminary purification.
Synthesis of manganese complex 1. A solution of 1 equivalent of 2-aminomethyl-pyridine (5 mmol, 0.54 g) in 3 mL of THF was dropwise added to a solution of 1 equivalent of acenaphthenequinone (5 mmol, 0.91 g) in 30 mL of THF. The reaction mixture was stirred at room temperature for about 24 h. Then, metallic sodium (1.1 equiv., 0.0023 g) was added and the solution was stirred for another 24 h. After that, manganese(II) bromide was added in one portion to the reaction mixture and, after 3 h of intense stirring, the solution was filtered. The filtrate was concentrated under a vacuum.
Single-crystal X-ray diffraction. The monocrystal analyzed was obtained by slow diffusion of n-hexane in THF at −35 °C. The diffraction data of 1 were registered on a Bruker D8 QUEST diffractometer with a PHOTON III area detector and an IμS DIAMOND microfocus X-ray tube using Mo Kα (0.71073 Å) radiation at 105(2) K. The data reduction package APEX4 was used for data processing. The data collected were corrected for systematic errors and absorption: empirical absorption correction based on spherical harmonics according to the Laue symmetry 1 ¯ using equivalent reflections. The structure was solved by the direct methods using SHELXT-2018/2 [18] and refined by the full-matrix least-squares on F2 using SHELXL-2018/3 [19]. Non-hydrogen atoms were refined anisotropically. The hydrogen atoms were found by Fourier maps, inserted at the calculated positions, and refined as riding atoms.
Crystallographic data for 1. C58H47Br2Mn2N5O4.5, plate (0.098 × 0.012 × 0.007 mm3), formula weight 1155.70 g mol−1; triclinic, P 1 ¯ (No. 2), a = 11.4754(3) Å, b = 13.0017(4) Å, c = 16.9515(5) Å, α = 90.9576(10)°, β = 103.9529(10)°, γ = 90.4510(11)°, V = 2454.01(12) Å3, Z = 2, Z’ = 1, T = 105(2) K, dcalc = 1.564 g cm−3, μ(Mo Kα) = 2.199 mm−1, F(000) = 1172; Tmax/min = 0.9281/0.8469; 64665 reflections were collected (1.945° ≤ θ ≤ 25.349°, index ranges: −13 ≤ h ≤ 13, −15 ≤ k ≤ 15, and −20 ≤ l ≤ 20), 8993 of which were unique, Rint = 0.0749, Rσ = 0.0455; completeness to θ of 25.349° 100.0%. The refinement of 713 parameters with 324 restraints converged to R1 = 0.0430 and wR2 = 0.1065 for 6802 reflections with I > 2σ(I) and R1 = 0.0636 and wR2 = 0.1180 for all data with goodness-of-fit S = 1.057 and residual electron density ρmax/min = 1.091 and −0.565 e Å−3, rms 0.091; max shift/e.s.d. in the last cycle 0.001.
Deposition number CCDC 2244472 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service www.ccdc.cam.ac.uk/structures (accessed on 24 February 2023).

4. Conclusions

Thus, a new binuclear manganese complex with two different N,O-ligands was obtained and structurally characterized by single-crystal X-ray diffraction. An interesting ligand environment near two manganese centers possibly makes this complex promising for further application in small molecule activation reactions.

Supplementary Materials

The following supporting information can be downloaded: EPR spectrum, 1H NMR spectrum, and crystallographic data in Crystallographic Information File (CIF) format.

Author Contributions

V.V.K., conceptualization, investigation, writing—original draft preparation; R.R.F., conceptualization, formal analysis, investigation, writing—original draft preparation, visualization, data curation; Y.H.B., writing—review and editing, supervision. All authors discussed and approved the final version. All authors have read and agreed to the published version of the manuscript.

Funding

The work was supported by the Russian Science Foundation (Grant No. 21-73-10186). The authors gratefully acknowledge the Assigned Spectral Analytical Center of FRC Kazan Scientific Center of RAS for providing the necessary facilities to carry out physical-chemical measurements.

Data Availability Statement

Data are contained within the article and the Supplementary Materials.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Gasperini, M.; Ragaini, F.; Cenini, S. Synthesis of Ar-BIAN Ligands (Ar-BIAN = Bis(aryl)acenaphthenequinonediimine) Having Strong Electron-Withdrawing Substituents on the Aryl Rings and Their Relative Coordination Strength toward Palladium(0) and -(II) Complexes. Organometallics 2002, 21, 2950–2957. [Google Scholar] [CrossRef]
  2. Fedushkin, I.L.; Kazarina, O.V.; Lukoyanov, A.N.; Skatova, A.A.; Bazyakina, N.L.; Cherkasov, A.V.; Palamidis, E. Mononuclear dpp-Bian Gallium Complexes: Synthesis, Crystal Structures, and Reactivity toward Alkynes and Enones. Organometallics 2015, 34, 1498–1506. [Google Scholar] [CrossRef]
  3. Gottumukkala, A.L.; Teichert, J.F.; Heijnen, D.; Eisink, N.; Dijk, S.; Ferrer, C.; Hoogenband, A.; Minnaard, A.J. Pd-Diimine: A Highly Selective Catalyst System for the Base-Free Oxidative Heck Reaction. J. Org. Chem. 2011, 76, 3498–3501. [Google Scholar] [CrossRef] [PubMed]
  4. Villa, M.; Miesel, D.; Hildebrandt, A.; Ragaini, F.; Schaarschmidt, D.; Wangelin, A.J. Synthesis and Catalysis of Redox-Active Bis(imino)acenaphthene (BIAN) Iron Complexes. ChemCatChem 2017, 9, 3203–3209. [Google Scholar] [CrossRef]
  5. Hazari, A.S.; Ray, R.; Hoque, M.A.; Lahiri, G.K. Electronic Structure and Multicatalytic Features of Redox-Active Bis(arylimino)acenaphthene (BIAN)-Derived Ruthenium Complexes. Inorg. Chem. 2016, 55, 8160–8173. [Google Scholar] [CrossRef] [PubMed]
  6. Soshnikov, I.E.; Bryliakov, K.P.; Antonov, A.A.; Sun, W.-H.; Talsi, E.P. Ethylene Polymerization of Nickel Catalysts with α-Diimine Ligands: Factors Controlling the Structure of Active Species and Polymer Properties. Dalton Trans. 2019, 48, 7974–7984. [Google Scholar] [CrossRef] [PubMed]
  7. Yambulatov, D.S.; Nikolaevskii, S.A.; Kiskin, M.A.; Magdesieva, T.V.; Levitskiy, O.A.; Korchagin, D.V.; Efimov, N.N.; Vasil’ev, P.N.; Goloveshkin, A.S.; Sidorov, A.A.; et al. Complexes of Cobalt(II) Iodide with Pyridine and Redox Active 1,2-Bis(arylimino)acenaphthene: Synthesis, Structure, Electrochemical, and Single Ion Magnet Properties. Molecules 2020, 25, 2054. [Google Scholar] [CrossRef] [PubMed]
  8. Yambulatov, D.S.; Nikolaevskii, S.A.; Kiskin, M.A.; Kholin, K.V.; Khrizanforov, M.N.; Yu, G.; Babeshkin, K.A.; Efimov, N.N.; Goloveshkin, A.S.; Imshennik, V.K.; et al. Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine. Molecules 2021, 26, 2998. [Google Scholar] [CrossRef] [PubMed]
  9. Hay, M.A.; Janetzki, J.T.; Kumar, V.J.; Gable, R.W.; Clérac, R.; Starikova, A.A.; Low, P.J.; Boskovic, C. Modulation of Charge Distribution in Cobalt-α-Diimine Complexes toward Valence Tautomerism. Inorg. Chem. 2022, 61, 17609–17622. [Google Scholar] [CrossRef] [PubMed]
  10. Kaim, V.; Kaur-Ghumaan, S. Manganese Complexes: Hydrogen Generation and Oxidation. Eur. J. Inorg. Chem. 2019, 2019, 5041–5051. [Google Scholar] [CrossRef]
  11. Moore, J.A.; Vasudevan, K.; Hill, N.J.; Reeske, G.; Cowley, A.H. Facile routes to Alkyl-BIAN ligands. Chem. Commun. 2006, 27, 2913–2915. [Google Scholar] [CrossRef] [PubMed]
  12. Ragaini, F.; Gasperini, M.; Parma, P.; Gallo, E.; Casati, N.; Macchi, P. Stability-inducing strain: Application to the synthesis of alkyl-BIAN ligands (alkyl-BIAN = bis(alkyl)acenaphthenequinonediimine). New J. Chem. 2006, 30, 1046–1057. [Google Scholar] [CrossRef]
  13. Ragaini, F.; Gasperini, M.; Gallo, E.; Macchi, P. Using ring strain to inhibit a decomposition path: First synthesis of an Alkyl-BIAN ligand (Alkyl-BIAN = bis(alkyl)acenaphthenequinonediimine). Chem. Commun. 2005, 1031–1033. [Google Scholar] [CrossRef] [PubMed]
  14. Hagar, M.; Ragaini, F.; Monticelli, E.; Caselli, A.; Macchi, P.; Casati, N. Chiral cyclopropylamines in the synthesis of new ligands; first asymmetric Alkyl-BIAN compounds. Chem. Commun. 2010, 46, 6153–6155. [Google Scholar] [CrossRef] [PubMed]
  15. Tsuge, O.; Tashiro, M. Studies of Acenaphthene Derivatives. XI. The Reaction of Acenaphthenequinone with Aliphatic Amines. Bull. Chem. Soc. Jpn. 1965, 38, 399–402. [Google Scholar] [CrossRef] [Green Version]
  16. Tsuge, O.; Tashiro, M. Studies of Acenaphthene Derivatives. XII. On the Red Substance Obtained from Acenaphthenequinone and Ammonia. Bull. Chem. Soc. Jpn. 1966, 39, 2477–2479. [Google Scholar] [CrossRef] [Green Version]
  17. Addison, A.W.; Rao, T.N.; Reedijk, J.; van Rijn, J.; Verschoor, G.C. Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate. J. Chem. Soc. Dalton Trans. 1984, 7, 1349–1356. [Google Scholar] [CrossRef]
  18. Sheldrick, G.M. SHELXT—Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr. Sect. A Found. Adv. 2015, 71, 3–8. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  19. Sheldrick, G.M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. C Struct. Chem. 2015, 71, 3–8. [Google Scholar] [CrossRef] [PubMed] [Green Version]
Scheme 1. Possible by-products of the reaction between aliphatic amine and AQ according to the literature.
Scheme 1. Possible by-products of the reaction between aliphatic amine and AQ according to the literature.
Molbank 2023 m1606 sch001
Scheme 2. Synthesis of binuclear manganese complex 1.
Scheme 2. Synthesis of binuclear manganese complex 1.
Molbank 2023 m1606 sch002
Figure 1. Molecular structure of 1 in the crystal with thermal ellipsoids at the 50% probability level according to single-crystal X-ray diffraction. Hydrogen atoms and solvent molecules are omitted for clarity. Selected interatomic distances [Å]: Br1–Mn1 2.4871(7), Mn1–O1 2.316(3), Mn1–O2 2.031(3), Mn1–N1 2.191(3), Mn1–N2 2.265(3), Br2–Mn2 2.5335(7), Mn2–O1 2.208(3), Mn2–O2 2.139(3), Mn2–O3 2.199(3), Mn2–N3 2.493(3), Mn2–N5 2.264(4).
Figure 1. Molecular structure of 1 in the crystal with thermal ellipsoids at the 50% probability level according to single-crystal X-ray diffraction. Hydrogen atoms and solvent molecules are omitted for clarity. Selected interatomic distances [Å]: Br1–Mn1 2.4871(7), Mn1–O1 2.316(3), Mn1–O2 2.031(3), Mn1–N1 2.191(3), Mn1–N2 2.265(3), Br2–Mn2 2.5335(7), Mn2–O1 2.208(3), Mn2–O2 2.139(3), Mn2–O3 2.199(3), Mn2–N3 2.493(3), Mn2–N5 2.264(4).
Molbank 2023 m1606 g001
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Khrizanforova, V.V.; Fayzullin, R.R.; Budnikova, Y.H. Manganese(II) Bromide Coordination toward the Target Product and By-Product of the Condensation Reaction between 2-Picolylamine and Acenaphthenequinone. Molbank 2023, 2023, M1606. https://doi.org/10.3390/M1606

AMA Style

Khrizanforova VV, Fayzullin RR, Budnikova YH. Manganese(II) Bromide Coordination toward the Target Product and By-Product of the Condensation Reaction between 2-Picolylamine and Acenaphthenequinone. Molbank. 2023; 2023(1):M1606. https://doi.org/10.3390/M1606

Chicago/Turabian Style

Khrizanforova, Vera V., Robert R. Fayzullin, and Yulia H. Budnikova. 2023. "Manganese(II) Bromide Coordination toward the Target Product and By-Product of the Condensation Reaction between 2-Picolylamine and Acenaphthenequinone" Molbank 2023, no. 1: M1606. https://doi.org/10.3390/M1606

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop