Manganese(Ⅱ) and Copper(Ⅰ) Compounds Based on Two Derivatives of Imidazo[1, 5-a]pyridine: Synthesis, Structures, Magnetic Properties, and Catalytic Activity

Qian ZHANG Yan-Feng CUI Xia-Mei ZHANG Ya-Hong LI Jin-Lei YAO

Citation:  Qian ZHANG, Yan-Feng CUI, Xia-Mei ZHANG, Ya-Hong LI, Jin-Lei YAO. Manganese(Ⅱ) and Copper(Ⅰ) Compounds Based on Two Derivatives of Imidazo[1, 5-a]pyridine: Synthesis, Structures, Magnetic Properties, and Catalytic Activity[J]. Chinese Journal of Structural Chemistry, 2022, 41(3): 2203148-2203154. doi: 10.14102/j.cnki.0254-5861.2011-3296 shu

Manganese(Ⅱ) and Copper(Ⅰ) Compounds Based on Two Derivatives of Imidazo[1, 5-a]pyridine: Synthesis, Structures, Magnetic Properties, and Catalytic Activity

English

  • The coordination complexes of manganese(Ⅱ) and copper(Ⅰ) ions have been the subject of intensive research owing to their aesthetically pleasing structures, and intriguing physicochemical properties which are closely relevant to the design of new magnetic[1-10] and catalytic[11-20] materials. Coordination compounds chelated by derivatives of imidazo-[1, 5-a]pyridine were widely investigated in recent years[21-23]. This series of ligands possess several nitrogen donors, and they are electron rich and highly conjugated. These features render them to be the suitable ligands for assembling versatile coordination complexes. Recent advances in this area revealed that the complexes supported by this series of ligands exhibited potential applications in DNA cleavage[24-25], catalysis[26-27], and photoluminescent materials[28-30]. Therefore, the development of efficient synthetic methodologies for both imidazo[1, 5-a]pyridine scaffolds and their complexes is of great importance.

    With the motivations for synthesizing manganese(Ⅱ) and copper(Ⅰ) coordination complexes, and comprehensively studying the magnetic properties and catalytic activity of these compounds, we carried out the reactions of manganese(Ⅱ) and copper(Ⅱ) salts with 2, 6-bis(imidazo[1, 5-a]-pyridin-3-yl)pyridine (bipp) and 3-(pyridin-2-yl)imidazo[1, 5-a]pyridine (pip). Two complexes with formulae [Mn(bipp)-(SO4)(H2O)]n (1) and [Cu(pip)2]ClO4 (2) were prepared (Scheme 1). The magnetic properties of 1 and catalytic activity of 2 toward ketalization reactions were investigated. Herein, the preparation and structures of compounds 1 and 2 were reported. The magnetic properties of 1 and catalytic behavior of 2 were also presented.

    Scheme 1

    Scheme 1.  Synthesis of compounds 1 (a) and 2 (b)

    All manipulations were conducted under solvothermal conditions in air. All solvents and reagents were available from chemical suppliers and used directly. 2, 6-Bis(imidazo-[1, 5-a]pyridin-3-yl)pyridine (bipp) and 3-(pyridin-2-yl)imidazo[1, 5-a]pyridine (pip) were prepared by following the reported procedures[21-23]. FT-IR spectroscopy studies were carried out on a Nicolet MagNa-IR 500 spectrometer with samples prepared as KBr disks. Elemental analyses of carbon, hydrogen and nitrogen atoms were performed with a Carlo-Erba EA1110 CHNO-S analyser. The magnetic susceptibilities of 1 were determined on an MPMS XL-7 SQUID magnetometer.

    2.2.1   Preparation of [Mn(bipp)(SO4)(H2O)]n (1)

    To a 10 mL thick glass tube were added MeOH (4 mL), bipp (0.1 mmol, 31 mg), and MnSO4·H2O (0.1 mmol, 17 mg). The tube was then sealed and heated to 90 ºС for 72 hours. Red block-shaped crystals of the product were obtained upon gradually cooling the reaction mixture to ambient temperature. These crystals were isolated, rinsed with MeOH and dried. The yield of the product was 95% calculated by MnSO4·H2O. Elemental analysis calcd. (%) for C19H15MnN5O5S: C, 47.51; H, 3.15; N, 14.58. Found (%): C, 47.59; H, 3.43; N, 14.63. Selected ATR IR data (cm−1): 3158 (w), 2159 (w), 1631 (w), 1604 (w), 1591 (m), 1573 (m), 1553 (m), 1482 (s), 1359 (m), 1308 (w), 1263 (m), 1256 (m), 1173 (w), 1134 (w), 1114 (m), 1071 (s), 1037 (m), 921 (w), 908 (m), 831 (m), 844 (w), 792 (m), 753 (m), 740 (m), 683 (s), 670 (s), 663 (m), 619 (m).

    2.2.2   Preparation of [Cu(pip)2]ClO4 (2)

    To a 10 mL thick glass tube were added MeOH (4 mL), DMF (1 mL), Cu(ClO4)2·6H2O (0.1 mmol, 17 mg) and pip (0.1 mmol, 20 mg). The tube was then sealed and heated to 90 ºС for 72 hours. Red block-shaped crystals of the product were obtained upon gradually cooling the reaction mixture to ambient temperature. These crystals were isolated, rinsed with EtOH and dried. The yield of the product was 70% calculated by Cu(ClO4)2·6H2O. Elemental analysis calcd. (%) for C24H18ClCuN6O4: C, 52.09; H, 3.28; N, 15.19. Found: C, 51.95; H, 3.21; N, 15.03. The main ATR IR data (cm−1): 1597 (m), 1474 (m), 1447 (w), 1407 (s), 1365 (m), 1260 (m), 1168 (m), 1084 (s), 1013 (w), 978 (w), 913 (w), 826 (w), 778 (m), 767 (m), 731 (m), 719 (m), 678 (m), 619 (m).

    To a 10 mL Schlenk flask were added ketone (1.4 mmol), ethylene glycol (1.4 mmol), toluene (1 mL) and compound 2 (2 mg). The reaction mixture was heated to reflux with a Dean-Stark being connected to the bottom of a condenser for 24 h. Then compound 2 was removed by filtration. The yields of the products were calculated by 1H NMR.

    Diffraction data measurements for these two compounds were carried out on a Bruker Smart Apex Ⅱ diffractometer at 296.15 K. SHELXS package was employed to solve the structures of 1 and 2[31]. All ordered non-hydrogen elements were refined anisotropically by full-matrix least-squares calculations against F2[32]. X-ray powder diffraction data were determined on a Rigaku D/Max-2500 diffractometer utilizing a graphite monochromator and a Cu-target tube.

    These two compounds were characterized by IR (Fig. S1), X-ray powder diffraction analysis (Fig. S3), and elemental analysis. The existence of the coordinated water in compound 1 was confirmed by measuring the TG curve (Fig. S2). The PXRD patterns of these two compounds (experimental and simulated PXRD patterns, Fig. S3) indicated that the phases of compounds 1 and 2 were pure. Compound 1 underwent several step weight loss. The first step from 25 to 225 ℃ was assigned to the removal of the coordinated H2O molecule (calcd.: 3.74%; found: ca. 3.75%), suggesting high thermal stability of 1.

    The structure refinement details and crystal data are listed in Table S1. The main interatomic distances and angles are collected in Table 1. The structures of 1 and 2 are presented in Figs. 1 and 2. The main crystallographic parameters are summarized in the following descriptions.

    Table 1

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) for 1 and 2
    DownLoad: CSV
    Compound 1
    Bond Dist. Bond Dist. Bond Dist.
    Mn(1)–O(1) 2.1638(18) Mn(1)–N(3) 2.239(2) Mn(1)–O(3)1 2.1682(18)
    Mn(1)–N(1) 2.249(2) Mn(1)–O(2) 2.143(2) Mn(1)–N(2) 2.288(2)
    1 x, 3/2–y, 1/2+z
    Angle (°) Angle (°) Angle (°)
    O(1)–Mn(1)–O(3)1 168.53(7) O(2)–Mn(1)–N(3) 108.38(8) N(3)–Mn(1)–N(2) 71.38(7)
    O(1)–Mn(1)–N(3) 90.74(7) O(2)–Mn(1)–N(1) 108.72(8) N(1)–Mn(1)–N(2) 71.52(7)
    O(1)–Mn(1)–N(1) 93.14(7) O(2)–Mn(1)–N(2) 179.64(8) S(1)–O(1)–Mn(1) 134.40(11)
    O(1)–Mn(1)–N(2) 95.25(7) N(3)–Mn(1)–N(1) 142.90(7) S(1)–O(3)–Mn(1)2 141.53(11)
    O(3)1–Mn(1)–N(3) 90.24(8) O(2)–Mn(1)–O(3)1 83.84(7) O(2)–Mn(1)–O(1) 85.01(8)
    O(3)1–Mn(1)–N(1) 92.96(8) O(3)1–Mn(1)–N(2) 95.89(7)
    1 x, 3/2–y, 1/2+z; 2 x, 3/2–y, 1/2+z
    Compound 2
    Bond Dist. Bond Dist. Bond Dist.
    Cu(1)–N(1) 2.0758(15) Cu(1)–N(2) 2.0022(14) Cu(1)–N(3) 2.0275(14)
    Cu(1)–N(4) 2.0702(15)
    Angle (°) Angle (°) Angle (°)
    N(2)–Cu(1)–N(1) 80.67(6) N(3)–Cu(1)–N(1) 111.22(6) N(2)–Cu(1)–N(4) 111.87(6)
    N(2)–Cu(1)–N(3) 146.19(6) N(3)–Cu(1)–N(4) 81.66(6) N(4)–Cu(1)–N(1) 136.87(6)

    Figure 1

    Figure 1.  (a) Asymmetric unit of compound 1. (b) Molecular structure of 1 showing the chain-like configuration and coordination polyhedrons of the Mn ions. Symmetry codes: A: x, 3/2–y, 1/2+z

    Figure 2

    Figure 2.  (a) Crystallographically determined structure of 2 with the ellipsoids of 30% probability level. (b) Coordination polyhedron of the CuI ion

    Compound 1 crystalizes in monoclinic space group P21/c. Mr = 480.36, a = 10.6615(6), b = 15.4762(8), c = 12.6476(7) Å, β =113.3130(10)°, Dc = 1.665 g/cm3, V = 1916.47(18) Å3, μ = 0.843 mm‑1, F(000) = 980, R = 0.0380, wR = 0.0977, and goodness-of-fit is 1.094. Each asymmetric unit contains one Mn ion, one bipp ligand, one SO42- group and a coordination water molecule (Fig. 1). The Mn center is coordinated by N1, N2 and N3 atoms from one bipp ligand, O1 and O3A atoms from two SO42- groups and O2 atom from coordinated H2O molecule, giving a [MnN3O3] core. Along the a axis, the adjacent Mn ions are bridged by one O-S-O unit from one SO42- anion. The Mn…Mn distance is 6.476 Å. Within compound 1, two similar mononuclear [Mn1A(bipp)(μ3-O)] and [Mn1B(bipp)(μ3-O)] units are bridged by the [MnN3O3] core in a mirror mode, leading to a chain structure of [Mn(bipp)(SO4)(H2O)]n (Fig. 1). The average Mn–N length is 2.259 Å, and it is larger than that of Mn–O distance (2.158 Å). The bond angles of the Mn ion from the axial position range from 71.38(7)° to 142.90(7)°, and bond angles from the bridged plane fall in the scope of 83.84(7)°~168.53(7)°. A slight distortion from the ideal octahedral structure with a CShM (continuous symmetry measurement) value of 3.237 was calculated by using SHAPE 2.1 software[33].

    Compound 2 crystalizes in triclinic space group P$\overline{1}$. Mr = 553.43, a = 7.3860(4), b = 10.5325(6), c = 14.5829(8) Å, α = 88.959(2)°, β =78.193(2)°, γ = 80.407(2)°, Dc = 1.679 g/cm3, V = 1094.77(10) Å3, μ = 1.168 mm‑1, F(000) = 564, R = 0.0322, wR = 0.0852, and goodness-of-fit is 1.050. Compound 2 is composed of one [Cu(pip)2]+ unit and one ClO4- counterion (Fig. 2). The CuI ion of [Cu(pip)2]+ unit is chelated by two pip ligands. Thus the CuI centre displays tetrahedron geometry. The distances of Cu–Npyridine bonds are 2.0758(14) and 2.0275(14) Å, respectively. The Cu–Nimidazole distances are 2.0702(15) and 2.0022(14) Å, respectively.

    Dc magnetic susceptibility values of 1 were determined between 1.8 and 300 K. The χmT product for two asymmetric units at 300 K is 8.04 cm3·K·mol-1 (Fig. 3). This number is smaller than that of expected. As the theoretical value for two non-interacted Mn ions is 8.75 cm3·K·mol-1 (g = 2.00, S = 5/2). Upon cooling from 300 to 70 K, the χmT value remains almost constant. With further cooling, the value of χmT sharply decreases to 1.56 cm3·K·mol-1 at 1.8 K, proving that Mn complex is antiferromagnetically coupled.

    Figure 3

    Figure 3.  χMT products of 1 between 1.8 and 300 K at 1000 Oe. The solid line represents the fitted values based on the model[34]

    To quantitatively assess the antiferromagnetical couplings in complex 1, we fitted the interactions of compound 1 by using the classical spin Heisenberg model (1-J) for a Mn2 compound[34].

    Fitting the magnetic susceptibilities of 1 using the reported model[34] gave g = 1.95 and J = –0.34 cm-1. The negative J value indicated weakly antiferromagnetic Mn…Mn couplings.

    Having the crystal structures of 1 and 2 in hand, we next studied the catalytic behavior of compound 2 for the ketalization reactions of various ketones. Ketalization reaction is an efficient methodology to protect carbonyl moiety of ketones[35]. Typically, ketalization reaction is catalyzed by a Lewis acid. As the CuI ion of 2 is four-coordinated, it may serve as a Lewis acid to activate the oxygen of the carbonyl group.

    The protection of carbonyl groups of several ketones by ethylene glycol was conducted in toluene at 110 ℃. As can be seen in Table 2, when the substrates are aliphatic ketones, namely, acetone, 2-butanone, acetyl acetone and cyclohexanone (entries 1~3, 5), compound 2 can efficiently catalyze the reactions, generating the protected ketones with the yields of 88% (Fig. S6), 97% (Fig. S7), 97% (Fig. S8) and 99% (Fig. S10), respectively. The catalytic activity of complex 2 toward aromatic ketones is lower. It is found that a yield of only 5% (Fig. S9) was given for acetophenone.

    Table 2

    Table 2.  Ketalization of Ketones Catalysed by 2
    DownLoad: CSV
    Entry Ketone Product Cat. (mol%) Yield (%)
    1 0.2 88
    2 0.2 97
    3 0.2 97
    4 0.2 5
    5 0.2 99

    In conclusion, two complexes [Mn(bipp)(SO4)(H2O)]n (1) and [Cu(pip)2]ClO4 (2) were synthesized and characterized. They display diverse structures. The magnetic properties of compound 1 were studied, revealing antiferromagnetic interactions between metal centers. Compound 2 was able to catalyze the ketalization reactions of aliphatic and aromatic ketones. It exhibited high activity towards the ketalization of aliphatic ketones.


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  • Scheme 1  Synthesis of compounds 1 (a) and 2 (b)

    Figure 1  (a) Asymmetric unit of compound 1. (b) Molecular structure of 1 showing the chain-like configuration and coordination polyhedrons of the Mn ions. Symmetry codes: A: x, 3/2–y, 1/2+z

    Figure 2  (a) Crystallographically determined structure of 2 with the ellipsoids of 30% probability level. (b) Coordination polyhedron of the CuI ion

    Figure 3  χMT products of 1 between 1.8 and 300 K at 1000 Oe. The solid line represents the fitted values based on the model[34]

    Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) for 1 and 2

    Compound 1
    Bond Dist. Bond Dist. Bond Dist.
    Mn(1)–O(1) 2.1638(18) Mn(1)–N(3) 2.239(2) Mn(1)–O(3)1 2.1682(18)
    Mn(1)–N(1) 2.249(2) Mn(1)–O(2) 2.143(2) Mn(1)–N(2) 2.288(2)
    1 x, 3/2–y, 1/2+z
    Angle (°) Angle (°) Angle (°)
    O(1)–Mn(1)–O(3)1 168.53(7) O(2)–Mn(1)–N(3) 108.38(8) N(3)–Mn(1)–N(2) 71.38(7)
    O(1)–Mn(1)–N(3) 90.74(7) O(2)–Mn(1)–N(1) 108.72(8) N(1)–Mn(1)–N(2) 71.52(7)
    O(1)–Mn(1)–N(1) 93.14(7) O(2)–Mn(1)–N(2) 179.64(8) S(1)–O(1)–Mn(1) 134.40(11)
    O(1)–Mn(1)–N(2) 95.25(7) N(3)–Mn(1)–N(1) 142.90(7) S(1)–O(3)–Mn(1)2 141.53(11)
    O(3)1–Mn(1)–N(3) 90.24(8) O(2)–Mn(1)–O(3)1 83.84(7) O(2)–Mn(1)–O(1) 85.01(8)
    O(3)1–Mn(1)–N(1) 92.96(8) O(3)1–Mn(1)–N(2) 95.89(7)
    1 x, 3/2–y, 1/2+z; 2 x, 3/2–y, 1/2+z
    Compound 2
    Bond Dist. Bond Dist. Bond Dist.
    Cu(1)–N(1) 2.0758(15) Cu(1)–N(2) 2.0022(14) Cu(1)–N(3) 2.0275(14)
    Cu(1)–N(4) 2.0702(15)
    Angle (°) Angle (°) Angle (°)
    N(2)–Cu(1)–N(1) 80.67(6) N(3)–Cu(1)–N(1) 111.22(6) N(2)–Cu(1)–N(4) 111.87(6)
    N(2)–Cu(1)–N(3) 146.19(6) N(3)–Cu(1)–N(4) 81.66(6) N(4)–Cu(1)–N(1) 136.87(6)
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    Table 2.  Ketalization of Ketones Catalysed by 2

    Entry Ketone Product Cat. (mol%) Yield (%)
    1 0.2 88
    2 0.2 97
    3 0.2 97
    4 0.2 5
    5 0.2 99
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  • 发布日期:  2022-03-01
  • 收稿日期:  2021-06-25
  • 接受日期:  2021-10-12
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