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Article

Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes

by
Yu Li
1,†,
Chumin Liang
1,†,
Xunzhong Zou
1,
Jinzhong Gu
2,
Marina V. Kirillova
3 and
Alexander M. Kirillov
3,4,*
1
Guangdong Research Center for Special Building Materials and Its Green Preparation Technology/Foshan Research Center for Special Functional Building Materials and Its Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China
2
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
3
Centro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
4
Research Institute of Chemistry, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya st., 117198 Moscow, Russia
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Catalysts 2021, 11(2), 204; https://doi.org/10.3390/catal11020204
Submission received: 26 December 2020 / Revised: 19 January 2021 / Accepted: 29 January 2021 / Published: 3 February 2021
(This article belongs to the Special Issue MOFs for Advanced Applications)
Browse Figures
Versions Notes

Abstract

:
Three 2D coordination polymers, [Cu2(µ4-dpa)(bipy)2(H2O)]n∙6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa) as a linker, as well as 2,2′-bipyridine (bipy) as a crystallization mediator. Compounds 1–3 were obtained as crystalline solids and fully characterized. The structures of 1–3 were established by single-crystal X-ray diffraction, revealing 2D metal-organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1–3 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.

Graphical Abstract

1. Introduction

Functional coordination polymers (CPs) and derived materials have been of a special focus in recent years owing to important structural characteristics of these compounds [1,2,3], intrinsic properties [4,5], and a broad diversity of applications [6,7,8,9,10] including in the field of catalysis [11,12,13,14,15,16,17]. The development of new catalytic systems incorporating coordination polymers with target structures and functionalities continues to be a challenging area, since the assembly of CPs can be affected by a diversity of factors. These include the nature of metal centers, organic linkers and supporting ligands, stoichiometry, and various reaction conditions [18,19,20,21,22,23,24].
Aromatic carboxylic acids with several COOH groups are the most common building blocks for constructing functional CPs [14,15,17,19]. Within a diversity of such carboxylic acids, semi-flexible linkers are especially captivating due to unique geometrical arrangements and conformational flexibility, which may lead to crystallization of unexpected metal-organic architectures [21,22,23,25].
On the other hand, cyanosilylation of carbonyl substrates is an interesting reaction for C-C bond formation [26,27], which is used for the preparation of cyanohydrins—key precursors for some pharmaceutical and fine chemistry products [28,29]. The use of transition metal complexes or coordination polymers in cyanosilylation reactions is gaining relevance as these compounds can behave as low-cost, efficient, and recyclable catalysts [25,30,31].
Considering our research focus on the design of CPs and catalytic systems on their basis [14,15,25], the main goal of this study consisted in the preparation of new metal-organic architectures, followed by their characterization and catalytic application in cyanosilylation of benzaldehydes. Thus, we selected an unexplored ether-linked tetracarboxylic acid, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa, Scheme 1), and tested it as a principal building block for generating copper(II), manganese(II), and zinc(II) CPs. The use of H4dpa as a linker can be justified by a number of relevant features of this tetracarboxylic acid. These features include (i) up to 9 possible sites for coordination (eight O-carboxylate sites and an O-ether site); (ii) two aromatic rings that can provide certain spatial flexibility and conformational adaptation owing to their separation by O-ether group; (iii) the fact that this carboxylic acid possesses good stability under hydrothermal conditions and remains little-explored in the synthesis of CPs.
Thus, this work reports on the hydrothermal synthesis, characterization, thermal behavior, crystal structures, and catalytic application of 2D CPs derived from H4dpa as a linker and bipy as a crystallization mediator. The obtained products [Cu2(µ4-dpa)(bipy)2(H2O)]n∙6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3) were also screened as potential catalysts for mild cyanosilylation of benzaldehydes into cyanohydrins. The influence of different reaction conditions and substrate scope was investigated, showing that the zinc(II) CP 3 is a particularly effective and recyclable heterogeneous catalyst.

2. Results and Discussion

2.1. Hydrothermal Synthesis

Aqueous medium mixtures composed of Cu(II), Mn(II), or Zn(II) chlorides with H4dpa as a linker, NaOH as a base for deprotonation of carboxylic acid groups, and 2,2′-bipyridine as a mediator of crystallization were subjected to hydrothermal synthesis (3 days, 160 °C), resulting in the formation of three 2D coordination polymers as crystalline solids. These were formulated as [Cu2(µ4-dpa)(bipy)2(H2O)]n·6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3) on the basis of standard solid-state characterization methods, namely infrared spectroscopy (IR), elemental analysis (EA), thermogravimetric analysis (TGA), powder (PXRD) and single-crystal X-ray diffraction. All compounds represent 2D metal-organic networks that are driven by ether-bridged tetracarboxylate nodes that show two distinct coordination modes, namely µ4-dpa4− in 1 and 3, or µ6-dpa4− in 2 (Scheme 2).

2.2. Structure of [Cu2(µ4-dpa)(bipy)2(H2O)]n·6H2O (1)

The structure of a 2D CP 1 (Figure 1) comprises two Cu(II) centers (Cu1, Cu2), one µ4-dpa4− linker, two bipy moieties, and one terminal H2O ligand per asymmetric unit. The Cu1 center is 4-coordinated and exhibits a distorted {CuN2O2} seesaw geometry. It is formed by two carboxylate O atoms from a pair of µ4-dpa4− ligands and two bipy N atoms (Figure 1a). The Cu2 atom is five-coordinated and features a distorted {CuN2O3} square-pyramidal geometry. It is constructed from two oxygen atoms from two µ4-dpa4− blocks, two bipy N atoms, and a terminal H2O ligand.
The Cu–O [1.942(2)–2.345(3) Å] and Cu–N [1.992(3)–2.058(3) Å] bonds are typical for such a type of compounds [14,18,30]. The dpa4− ligand behaves as a µ4-linker with carboxylate moieties being monodentate (Scheme 2, mode I). In μ4-dpa4−, a dihedral angle between aromatic cycles and a Car–Oether–Car angle are 86.34 and 115.93°, correspondingly. The μ4-dpa4− linkers connect four Cu atoms to assemble a 2D metal-organic layer (Figure 2b) which, after simplification, is described as a mononodal 4-linked net. It possesses a sql (Shubnikov tetragonal plane net) topology with a (44.62) point symbol (Figure 1c) [32,33].

2.3. Structure of [Mn2(µ6-dpa)(bipy)2]n (2)

The structure of 2 also shows a 2D coordination polymer network (Figure 2). Per asymmetric unit, there are two manganese(II) atoms, one µ6-dpa4− block, and two bipy ligands. The Mn1 center is five-coordinated and shows a distorted {MnN2O3} trigonal-bipyramidal environment. It is built from three oxygen atoms from three µ6-dpa4− linkers and a pair of bipy N donors (Figure 2a). The six-coordinate Mn2 center is bound by four oxygen atoms from three µ6-dpa4− ligands and a pair of bipy N atoms, thus creating a distorted {MnN2O4} octahedral geometry. The Mn–O [2.087(3)–2.217(4) Å] and Mn–N [2.226(4)–2.277(4) Å] bonds agree with those in related compounds [19,21,22]. The tetracarboxylate dpa4− moiety behaves as a μ6-linker (Scheme 2, mode II) with the carboxylate functionalities being monodentate or µ-bridging bidentate. In μ6-dpa4−, the relevant angles are 79.83° (dihedral angle among aromatic moieties) and 116.37° (Car–Oether–Car). The manganese(II) centers are held together by three carboxylate groups from three μ6-dpa4− blocks, thus generating a dimanganese(II) subunit [Mn1∙Mn2 3.4679(6) Å] (Figure 2b). Such Mn2 subunits are additionally connected by carboxylate groups of μ6-dpa4− to form a 2D metal-organic layer (Figure 2c). Regarding topology, this 2D layer is built from 3-linked Mn1/Mn2 nodes as well as the 6-linked µ6-dpa4− nodes (Figure 2d). The resulting net is thus classified as a binodal 3,6-linked layers of a 3,6L66 topological type [34]. It is described by a (43.612)(43)2 point symbol, wherein the (43.612) and (43) indices correspond to the Mn(II) and µ6-dpa4− nodes, respectively.

2.4. Structure of [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2H2O (3)

In the structure of a 2D coordination polymer 3 (Figure 3), there are two zinc(II) atoms (Zn1, Zn2), one µ4-dpa4− block, two bipy moieties, two terminal water ligands and a couple of lattice H2O molecules. Both Zn atoms are five-coordinated, showing distorted {ZnN2O3} square pyramidal geometries. These are constructed from two O donors from a pair of µ4-dpa4− linkers, a water ligand, and a pair of bipy nitrogen atoms. The Zn–O [1.973(3)–2.093(4) Å] and Zn–N [2.119(3)–2.181(3) Å] bond lengths are typical for compounds having an O–Zn–N environment [2,30,35,36]. The dpa4− block adopts a µ4-coordination fashion (Scheme 2, mode I). In µ4-dpa4−, the relevant angles are 72.59° (dihedral angle among two aromatic moieties) and 117.72° (Car–Oether–Car). The µ4-dpa4− blocks interconnect four Zn(II) centers to furnish a 2D layer (Figure 3b). Its topological classification discloses an uninodal 3-linked layer with an hcb (Shubnikov hexagonal plane net/(6, 3)) topology and a (63) point symbol (Figure 3c) [37,38].

2.5. TGA & PXRD

Thermal behavior of compounds 1–3 was investigated by TGA on gradual heating from 30 to 800 °C under nitrogen flow (Figure S2). CP 1 reveals a loss of six lattice and one coordinated H2O molecules in the 33–104 °C interval (calcd. 13.8%; exptl. 13.5%). After dehydration, the network of 1 maintains its stability until 220 °C. CP 2 does not encompass water as a lattice solvent or ligand and shows thermal stability up to 338 °C. For CP 3, a mass loss in the 86–171 °C window refers to an elimination of two crystallization and two coordinated H2O moieties (calcd. 8.4%; exptl. 8.6%); the obtained sample maintains stability until 218 °C.
To confirm a phase purity, the microcrystalline powders of 1–3 were analyzed by PXRD (Figure S2). The obtained experimental plots well agree with the patterns calculated from single-crystal X-ray diffraction data, what confirms a purity of the bulk solids 1–3 prepared via hydrothermal synthetic procedure.

2.6. Cyanosilylation of Benzaldehydes

Coordination polymers 1−3 were tested as catalysts in the mild, heterogeneous cyanosilylation of benzaldehyde substrates with TMSCN (trimethylsilyl cyanide) [33,35]. 4-Nitrobenzaldehyde was used as model substrate and converted into the corresponding cyanohydrin product, 2-(4-nitrophenyl)-2-[(trimethylsilyl)oxy]acetonitrile (Table 1, Scheme 3). An influence of catalyst loading, solvent type, reaction time, catalyst recycling and substrate scope was investigated.
The cyanosilylation reaction almost does not undergo when catalyst is absent or when using a carboxylic acid ligand or a metal salt precursor as potential catalysts (3−8% yields; Table 1, entries 1−3). The product yields are higher when using 1 (37%, entry 4) and 2 (27%, entry 5) as catalysts, and significantly higher in the presence of 3 (92%, entry 6). Although it is not possible to establish a clear relationship between structural features and catalytic activity of the obtained 2D compounds, we can speculate that a superior activity exhibited by the coordination polymer 3 may eventually be related to the presence of accessible and unsaturated zinc(II) centers on a surface of catalyst particles, together with a higher Lewis acidity of the zinc sites [30,39]. Given a superior activity of zinc(II) derivative 3, the reaction catalyzed by this CP was optimized further.
We found that there is an yield growth from 40 to 92% on increasing the time of reaction in the 1–12 h interval (Table 1, entries 6−12; Figure S7). The catalyst 3 loading of 2, 3, or 4 mol% has also a notable effect as attested by an yield increase from 73 to 92 and 93%, respectively (entries 6, 13, 14). Although dichloromethane (CH2Cl2) was used as a standard solvent to achieve the highest yield (92%), the cyanosilylation reaction also undergoes quite effectively in alternative solvents such as chloroform (CHCl3, 82%), tetrahydrofuran (THF, 68%), acetonitrile (CH3CN, 76%), and methanol (CH3OH, 80%) (Table 1, entries 15−18).
Furthermore, in the reactions catalyzed by 3, substrate scope was studied using different functionalized benzaldehydes (Table 2). The corresponding cyanohydrin products are obtained in yields ranging from 51 to 87%. The substrates with an electron-withdrawing group (R = NO2, Cl) generally show a higher reactivity (Table 2, entries 2−5), which can be explained by an increased substrate electrophilicity. As expected, benzaldehyde (R = H) and substrates with an electron-donating group (R = OH, CH3) reveal lower product yields (entries 6, 7).
Given a remarkable activity of CP 3 in these cyanosilylation reactions, the stability of the catalyst and its possible recycling were studied. Thus, in the end of the cyanosilylation of 4-nitrobenzaldehyde (conditions of entry 6, Table 1), the catalyst was isolated via centrifugation, washed by CH2Cl2, air-dried, and reused in the next reaction runs. These tests indicate that the coordination polymer 3 behaves as a stable catalyst which maintains its activity for a minimum of 4 cyanosilylation cycles, as attested by resembling product yields in the 92−87% range (Figure S8). In addition, PXRD data of the used catalyst (Figure S9) show that its metal-organic structure remains stable.

3. Experimental

3.1. Chemicals & Equipment

All chemicals were obtained from commercial sources. In particular, 3-(2′,4′-Dicarboxylphenoxy)phthalic acid (H4dpa) was acquired from Jinan Henghua Sci. & Tec. Co., Ltd. (Jinan, China). Infrared (IR) spectroscopy measurements (KBr discs) were performed on a Bruker EQUINOX 55 spectrometer (Bruker Corporation, Billerica, MA, USA). Elemental analyses (C, H, N) were carried out on an Elementar Vario EL device (Elementar, Langenselbold, Germany). LINSEIS STA PT1600 thermal analyzer (Linseis Messgeräte GmbH, Selb, Germany) was used for TGA (thermogravimetric analysis) measurements under N2 atmosphere at 10 °C/min heating rate. Excitation/emission spectroscopic data were obtained using an Edinburgh FLS920 fluorescence spectrometer (Edinburgh Instruments, Edinburgh, England). Rigaku-Dmax 2400 diffractometer (Cu-Kα radiation; λ = 1.54060 Å; Rigaku Corporation, Tokyo, Japan) was used to obtain powder X-ray diffraction (PXRD) patterns. Solution 1H NMR (nuclear magnetic resonance) spectra were measured on a JNM ECS 400M spectrometer (JEOL Ltd., Tokyo, Japan).

3.2. Hydrothermal Synthesis & Analytical Data

In a general procedure, metal(II) chloride (0.2 mmol: CuCl2·2H2O (34.1 mg) for 1, MnCl2·4H2O (39.6 mg) for 2, or ZnCl2 (27.3 mg) for 3), H4dpa (0.1 mmol, 34.6 mg), bipy (0.2 mmol, 31.2 mg), NaOH (0.4 mmol, 16.0 mg), and H2O (10 mL) were added into a Teflon-lined stainless steel vessel (volume: 25 mL) and stirred for 15 min at ambient temperature. Then, the vessel was closed and kept in an oven at 160 °C. After 3 days at this temperature, the vessel was gradually (10 °C/h) cooled down to ambient temperature. The reaction mixture was then transferred to a glass flask and the crystals of products were decanted or filtered off, followed by washing with H2O and drying in air to produce compounds 1−3.
[Cu2(µ4-dpa)(bipy)2(H2O)]n·6nH2O (1). Blue block-shaped crystals, yield: 55% based on H4dpa. Calcd for C36H36Cu2N4O16: C 47.63, H 4.00, N 6.17%. Found: C 47.86, H 3.98, N 6.21%. IR (KBr, cm−1): 3748 w, 3082 w, 1599 s, 1568 s, 1497 w, 1475 w, 1448 m, 1368 s, 1288 w, 1240 m, 1164 w, 1137 w, 1084 w, 1062 w, 1032 w, 974 w, 921w, 854 w, 823 w, 770 m, 735w, 663 w.
[Mn2(µ6-dpa)(bipy)2]n(2). Yellow block-shaped crystals, yield: 52% based on H4dpa. Calcd for C36H22Mn2N4O9: C 56.56, H 2.90, N 7.33%. Found: C 56.37, H 2.89, N 7.38%. IR (KBr, cm−1): 1639 s, 1598 s, 1569 m, 1470 w, 1438 w, 1376 s, 1240 m, 1182 w, 1157 w,1128 w, 1087 w, 1063 w, 1013 w, 968 w, 923 w, 848 w, 820 w, 770 m, 736 w, 696 w, 675 w, 646 w.
[Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3). Colorless block-shaped crystals, yield: 48% based on H4dpa. Calcd for C36H30Zn2N4O13: C 50.43, H 3.53, N 6.53%. Found: C 50.64, H 3.55, N 6.51%. IR (KBr, cm−1): 3383 w, 3106 w, 1614 s, 1569 s, 1470 m, 1438 s, 1392 s, 1322 w, 1244 w, 1157 w, 1083 w, 1063 w, 1021 w, 972 w, 918 w, 877 w, 766 m, 733 w, 687 w, 650 w.

3.3. Single-Crystal X-ray Diffraction

For CPs 1–3, data were collected on a Bruker APEX-II CCD diffractometer (Bruker, Karlsruhe, Germany) (graphite-monochromated CuKα radiation, λ = 1.54178 Å). SADABS was used for semi-empirical absorption corrections. Crystal structures were determined by direct methods, followed by the refinement (full-matrix least-squares on F2) with SHELXS-97 and SHELXL-97 [40]. With an exception of hydrogen atoms, all other atoms were subjected to an anisotropic refinement (full-matrix least-squares on F2). Except hydrogen atoms in water, all H atoms were placed in calculated positions (fixed isotropic thermal parameters); these were taken into account at the final stage of full-matrix least-squares refinement in structure factor calculations. Water hydrogen atoms were found by difference maps and constrained to the respective oxygen centers. In 1, some molecules of solvent are heavily disordered and thus were detached by applying SQUEEZE in PLATON [41]. Elemental and thermogravimetric analyses confirmed the number of crystallization H2O molecules. For 1–3, final crystal data are summarized in Table 3. Representative bond distances and angles (Table S1) as well as hydrogen bond parameters (Table S2) are listed in Supplementary Materials. CCDC-2043757–2043759 contain crystallographic data for 1–3.
For topological analysis of 2D layers in 1–3, an underlying net concept was followed [42]. Such simplified networks were constructed by reducing bridging ligands to their centroids and removing terminal ligands, preserving a ligand–metal center connectivity.

3.4. Catalytic Cyanosilylation

Typical reaction mixtures were prepared as follows: in a small vessel, solid catalyst (typically 3 mol%) was suspended in dichloromethane (2.5 mL) and then an aldehyde substrate (0.50 mmol) and a cyanosilylation agent trimethylsilyl cyanide (1.0 mmol) were added. The reaction was kept under stirring at room temperature (~25 °C) for the desired time. Then, the catalyst was separated by centrifugation and the filtrate was subjected to solvent evaporation under reduced pressure to form a crude solid. This solid was dissolved in CDCl3 and analyzed by 1H NMR spectroscopy for product quantification (for details, see Supplementary Materials, Figures S5 and S6). In the catalyst recycling experiments, the catalyst was centrifuged, washed with CH2Cl2, dried at room temperature, and reused in subsequent steps that were done as described above. Blank tests without any catalyst or using metal salt or H4dpa as catalyst were also carried out for comparative purposes.

4. Conclusions

In this study, we explored a still poorly studied tetracaboxylic acid, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa), as a multifunctional linker for the hydrothermal synthesis of new CPs. Hence, a simple synthetic procedure led to the formation of a series of copper(II), manganese(II), and zinc(II) coordination polymers. These compounds feature distinct types of 2D metal-organic layers driven by the µ4-dpa4− or µ6-dpa4− linkers, as well as different topologies ranging from sql (1) and 3,6L66 (2) to hcb (3).
Catalytic activity of 1−3 was also explored in the mild cyanosilylation of benzaldehyde substrates with TMSCN, showing that the zinc(II) CP 3 functions as an effective and reusable heterogeneous catalyst to give cyanohydrin products in up to 93% yields. The effects of various reactions parameters as well as substrate scope were studied.
As main novelty features of this work, we can highlight (i) an application of H4dpa as an underexplored multifunctional linker for design of new CPs, (ii) a synthesis of three structurally and topologically distinct metal-organic architectures, and (iii) notable catalytic activity of a zinc(II) derivative in the cyanosilylation reactions. Besides, the obtained results widen the applications of coordination polymers in heterogeneous catalysis [43,44]. Further research on assembling related types of CPs and exploring their potential in other catalytic transformations are currently underway.

Supplementary Materials

The following data are available online at https://www.mdpi.com/2073-4344/11/2/204/s1. Figure S1: FT-IR spectra, Figure S2: TGA curves, Figures S3 and S9: PXRD patterns, Figure S4: emission spectra, Figures S5–S8: supplementary catalysis data, Tables S1 and S2: selected structural parameters for 1–3. CCDC-2043757–2043759.

Author Contributions

Conceptualization, J.G., X.Z. and A.M.K.; data curation, C.L., Y.L.; funding acquisition, Y.L., J.G. and A.M.K.; investigation, C.L., X.Z., Y.L., J.G. and M.V.K.; methodology, J.G.; visualization, J.G. and M.V.K.; writing—original draft, Y.L., J.G., X.Z., M.V.K. and A.M.K.; writing—review and editing, A.M.K. All authors have read and agreed to the published version of the manuscript.

Funding

This work has been supported by Science and Technology Planning Project of Guangzhou (201904010381), the Foundation for Science and Technology (FCT) and Portugal 2020 (projects CEECIND/03708/2017, LISBOA-01-0145-FEDER-029697, PTDC/QUI-QIN/3898/2020, and UID/QUI/00100/2013). This paper has been supported by the RUDN University Strategic Academic Leadership Program.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 11 00204 sch001 550
Scheme 1. Structural formulae of H4dpa and bipy.
Scheme 1. Structural formulae of H4dpa and bipy.
Catalysts 11 00204 sch001
Catalysts 11 00204 sch002 550
Scheme 2. Coordination modes of µ4- or µ6-dpa4− linkers in 1–3.
Scheme 2. Coordination modes of µ4- or µ6-dpa4− linkers in 1–3.
Catalysts 11 00204 sch002
Catalysts 11 00204 g001 550
Figure 1. Structural fragments of 1. (a) Coordination environment around Cu(II) atoms; H atoms are omitted for clarity. Symmetry codes: i = x + 1, y, z + 1; ii = x + 1, y, z. (b) 2D metal-organic layer; view along the b axis. (c) Topological view of 2D layer with a sql topology; view along the b axis; Cu centers (green balls), centroids of µ4-dpa4− nodes (gray).
Figure 1. Structural fragments of 1. (a) Coordination environment around Cu(II) atoms; H atoms are omitted for clarity. Symmetry codes: i = x + 1, y, z + 1; ii = x + 1, y, z. (b) 2D metal-organic layer; view along the b axis. (c) Topological view of 2D layer with a sql topology; view along the b axis; Cu centers (green balls), centroids of µ4-dpa4− nodes (gray).
Catalysts 11 00204 g001
Catalysts 11 00204 g002 550
Figure 2. Structural fragments of 2. (a) Coordination environment around Mn(II) atoms; H atoms are omitted for clarity. Symmetry codes: i = x + 1, y, z; ii = x + 1, −y + 3/2, z + 1/2. (b) Mn2 subunit. (c) 2D metal-organic layer; view along the b axis. (d) Topological representation of 2D layer with a 3,6L66 topology; view along the b axis; Mn(II) nodes (turquoise balls), centroids of µ6-dpa4− nodes (gray).
Figure 2. Structural fragments of 2. (a) Coordination environment around Mn(II) atoms; H atoms are omitted for clarity. Symmetry codes: i = x + 1, y, z; ii = x + 1, −y + 3/2, z + 1/2. (b) Mn2 subunit. (c) 2D metal-organic layer; view along the b axis. (d) Topological representation of 2D layer with a 3,6L66 topology; view along the b axis; Mn(II) nodes (turquoise balls), centroids of µ6-dpa4− nodes (gray).
Catalysts 11 00204 g002
Catalysts 11 00204 g003 550
Figure 3. Structural fragments of 3. (a) Coordination environment around Zn(II) atoms; H atoms are omitted for clarity. Symmetry codes: i = −x, −y + 1, −z; ii = −x + 1/2, y − 1/2, −z + 1/2. (b) 2D metal-organic layer; view along the a axis. (c) Topological representation of 2D layer with an hcb topology; view along the a axis; Zn(II) centers (cyan balls), centroids of µ4-dpa4− nodes (gray).
Figure 3. Structural fragments of 3. (a) Coordination environment around Zn(II) atoms; H atoms are omitted for clarity. Symmetry codes: i = −x, −y + 1, −z; ii = −x + 1/2, y − 1/2, −z + 1/2. (b) 2D metal-organic layer; view along the a axis. (c) Topological representation of 2D layer with an hcb topology; view along the a axis; Zn(II) centers (cyan balls), centroids of µ4-dpa4− nodes (gray).
Catalysts 11 00204 g003
Catalysts 11 00204 sch003 550
Scheme 3. Cyanosilylation of model substrate(4-nitrobenzaldehyde) into the corresponding cyanohydrin.
Scheme 3. Cyanosilylation of model substrate(4-nitrobenzaldehyde) into the corresponding cyanohydrin.
Catalysts 11 00204 sch003
Table
Table 1. Cyanosilylation of 4-nitrobenzaldehyde with TMSCN catalyzed by coordination polymers. a
Table 1. Cyanosilylation of 4-nitrobenzaldehyde with TMSCN catalyzed by coordination polymers. a
EntryCatalystTime, hCatalyst Loading, mol%SolventYield b, %
1blank12-CH2Cl23
2H3dpna123.0CH2Cl26
3ZnCl2123.0CH2Cl28
41123.0CH2Cl237
52123.0CH2Cl227
63123.0CH2Cl292
7313.0CH2Cl240
8323.0CH2Cl262
9343.0CH2Cl273
10363.0CH2Cl280
11383.0CH2Cl284
123103.0CH2Cl288
133122.0CH2Cl273
143124.0CH2Cl293
153123.0CHCl382
163123.0CH3CN76
173123.0THF68
183123.0CH3OH80
a Conditions: 4-nitrobenzaldehyde (0.5 mmol), TMSCN (1.0 mmol), solvent (2.5 mL), room temperature (~25 °C). b Yields based on 1H NMR (nuclear magnetic resonance) analysis: (moles of product per mol of benzaldehyde substrate) × 100%.
Table
Table 2. Substrate scope in cyanosilylation of various benzaldehydes with TMSCN catalyzed by 3. a
Table 2. Substrate scope in cyanosilylation of various benzaldehydes with TMSCN catalyzed by 3. a
Catalysts 11 00204 i001
EntrySubstrate (R-C6H4CHO)Yield b, %
1R = H61
2R = 2-NO282
3R = 3-NO287
4R = 4-NO292
5R = 4-Cl62
6R = 4-OH56
7R = 4-CH351
a Conditions: functionalized benzaldehyde (0.5 mmol), TMSCN (1.0 mmol), catalyst 3 (3.0 mol.%), CH2Cl2 (2.5 mL), room temperature (~25 °C). b Yields based on 1H NMR analysis: (moles of product per mol of functionalized benzaldehyde substrate) × 100%.
Table
Table 3. Crystal data for CPs 1−3.
Table 3. Crystal data for CPs 1−3.
Compound123
Chemical formulaC36H36Cu2N4O16C36H22Mn2N4O9C36H30Zn2N4O13
Molecular weight907.78764.45857.38
Crystal systemMonoclinicMonoclinicMonoclinic
Space groupP21/nP21/cP21/n
a/Å10.3607 (5)10.5312 (3)7.9352 (2)
b/Å35.8638 (11)21.2195 (5)13.1264 (4)
c/Å11.3823 (5)15.1835 (4)34.5048 (10)
α/(°)909090
β/(°)116.385 (6)107.751 (3)94.158 (3)
γ/(°)909090
V/Å3788.8 (3)3231.47 (17)3584.58 (18)
Z444
F (000)162415521752
Crystal size/mm0.25 × 0.23 × 0.210.18 × 0.16 × 0.150.26 × 0.24 × 0.20
θ range for data collection4.508–69.9933.699–66.9923.604–70.060
Limiting indices−12 ≤ h ≤ 12, −43 ≤ k ≤ 30, −13 ≤ l ≤ 13−12 ≤ h ≤ 11, −25 ≤ k≤ 25, −18 ≤ l ≤ 17−8 ≤ h ≤ 9, −1 ≤ 15, −41 ≤ l ≤ 40
Reflections collected/unique (Rint)19,512/7079 (0.0494)20,432/5753 (0.0993)13,030/6658 (0.0337)
Dc/(Mg·cm−3)1.4021.5711.589
μ/mm−11.8926.9172.285
Data/restraints/parameters7079/0/4695753/0/4606658/0/496
Goodness-of-fit on F21.0471.0741.017
Final R indices [(I ≥ 2σ(I))] R1, wR20.0537, 0.14440.0707, 0.16800.0515, 0.1169
R indices (all data) R1, wR20.0710, 0.15460.0901, 0.18000.0619, 0.1238
Largest diff. peak and hole/(e·Å−3)1.195 and −0.6480.859 and −1.0890.857 and −1.096
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Li, Y.; Liang, C.; Zou, X.; Gu, J.; Kirillova, M.V.; Kirillov, A.M. Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes. Catalysts 2021, 11, 204. https://doi.org/10.3390/catal11020204

AMA Style

Li Y, Liang C, Zou X, Gu J, Kirillova MV, Kirillov AM. Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes. Catalysts. 2021; 11(2):204. https://doi.org/10.3390/catal11020204

Chicago/Turabian Style

Li, Yu, Chumin Liang, Xunzhong Zou, Jinzhong Gu, Marina V. Kirillova, and Alexander M. Kirillov. 2021. "Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes" Catalysts 11, no. 2: 204. https://doi.org/10.3390/catal11020204

APA Style

Li, Y., Liang, C., Zou, X., Gu, J., Kirillova, M. V., & Kirillov, A. M. (2021). Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes. Catalysts, 11(2), 204. https://doi.org/10.3390/catal11020204

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