Synthesis, Characterizations and Chemometric Analysis Approach of Nitrile Functionalized Asymmetrical Dinuclear Silver(I) Di-N¬-Heterocyclic Carbene Complexes
DOI:
https://doi.org/10.33736/jaspe.7677.2024Keywords:
N-heterocyclic carbene, Silver(I) complexes, Bis-benzimidazolium salts, Nitrile-functionalization, Principal component analysisAbstract
A series of novel asymmetrical bis-benzimidazolium salts were synthesized via a two-step alkylation process, yielding the benzimidazolium salts of N,N'-(ethane/propane/butane-1,2/3/4-diyl)-1-benzylbenzimidazolium-1'-(n-benzonitrile)benzimidazolium dibromide (n = 2,3,4) (1Br – 9Br). These salts served as carbene precursors for the subsequent formation of nitrile-functionalized asymmetrical silver(I) di-NHC complexes (Ag1 – Ag9) (NHC = N-heterocyclic carbene) through an in-situ deprotonation method using Ag2O. Comprehensive characterization of the bis-benzimidazolium salts and their corresponding dinuclear silver(I) di-NHC complexes was performed using melting point determination, CHN elemental analyses, FTIR, and 1H- and 13C-NMR spectroscopy. The successful complexation of nitrile-functionalized NHC ligands with silver(I) ions was evidenced by the disappearance of the acidic-carbene proton peak (δ 9.69 – 10.23 ppm) in the 1H-NMR spectra of the complexes. Furthermore, the formation of Ag-Ccarbene bonds was confirmed by the appearance of characteristic peaks in the 13C-NMR spectra of Ag1 – Ag9 (δ 170.89 – 195.90 ppm). To elucidate structure-property relationships, the Principal Component Analysis (PCA) was applied to the NMR spectroscopic data. The PCA of the 1H-NMR data revealed distinct clustering of bis-benzimidazolium salts and their respective silver(I) di-NHC complexes, with the first two principal components accounting for 71.40% of the total variance. Similarly, the PCA of the 13C-NMR data explained 72.08% of the total variance through the first two principal components. These results demonstrate the efficacy of PCA in differentiating and classifying the compounds based on their structural features and functional groups. Moreover, this study highlights the synergistic application of advanced spectroscopic techniques and chemometric analysis in inorganic synthesis chemistry subject and the insights gained from this approach contribute to a deeper understanding of the structural properties and potential applications of these novel NHC complexes, paving the way for future developments in organometallic chemistry and catalysis.
References
Jalal, M., Hammouti, B., Touzani, R., Aouniti, A., & Ozdemir, I. (2020). Metal-NHC Heterocycle Complexes in Catalysis and Biological Applications: Systematic Review. Materials Today: Proceedings, 31, S122-S129. https://doi.org/10.1016/j.matpr.2020.06.398
Li, J., He, D., Lin, Z., Wu, W., & Jiang, H. (2021). Recent Advances in NHC–Palladium Catalysis for Alkyne Chemistry: Versatile Synthesis and Applications. Organic Chemistry Frontiers, 8(13), 3502-3524. https://doi.org/10.1039/D1QO00111F
Wang, Z., Tzouras, N. V., Nolan, S. P., & Bi, X. (2021). Silver N-Heterocyclic Carbenes: Emerging Powerful Catalysts. Trends in Chemistry, 3(8), 674-685. https://doi.org/10.1016/j.trechm.2021.04.006
Ronga, L., Varcamonti, M., & Tesauro, D. (2023). Structure–Activity Relationships in NHC–Silver Complexes as Antimicrobial Agents. Molecules, 28(11), 4435. https://doi.org/10.3390/molecules28114435
Scattolin, T., & Nolan, S. P. (2020). Synthetic Routes to Late Transition Metal–NHC Complexes. Trends in Chemistry, 2(8), 721-736. https://doi.org/10.1016/j.trechm.2020.06.001
Nayak, S., & Gaonkar, S. L. (2021). Coinage Metal N‐Heterocyclic Carbene Complexes: Recent Synthetic Strategies and Medicinal Applications. ChemMedChem, 16(9), 1360-1390. https://doi.org/10.1002/cmdc.202000836
Şahin-Bölükbaşı, S., & Şahin, N. (2019). Novel Silver-NHC Complexes: Synthesis and Anticancer Properties. Journal of Organometallic Chemistry, 891, 78-84. https://doi.org/10.1016/j.jorganchem.2019.04.018
Romain, C., Bellemin-Laponnaz, S., & Dagorne, S. (2020). Recent Progress on NHC-Stabilized Early Transition Metal (Group 3–7) Complexes: Synthesis and Applications. Coordination Chemistry Reviews, 422, 213411. https://doi.org/10.1016/j.ccr.2020.213411
Werner, L., Horrer, G., Philipp, M., Lubitz, K., Kuntze‐Fechner, M. W., & Radius, U. (2021). A General Synthetic Route to NHC‐Phosphinidenes: NHC‐Mediated Dehydrogenation of Primary Phosphines. Zeitschrift für anorganische und allgemeine Chemie, 647(8), 881-895. https://doi.org/10.1002/zaac.202000405
Aktaş, A., Yakalı, G., Demir, Y., Gülçin, İ., Aygün, M., & Gök, Y. (2022). The Palladium-Based Complexes bearing 1,3-dibenzylbenzimidazolium with Morpholine, Triphenylphosphine, and Pyridine Derivate Ligands: Synthesis, Characterization, Structure and Enzyme Inhibitions. Heliyon, 8(9). https://doi.org/10.1016/j.heliyon.2022.e10625
Giarrusso, C. P., Zeil, D. V., & Blair, V. L. (2023). Catalytic exploration of NHC–Ag (i) HMDS Complexes for the Hydroboration and Hydrosilylation of Carbonyl Compounds. Dalton Transactions, 52(23), 7828-7835. https://doi.org/10.1039/D3DT01042B
Abdurrahman, N., Sasidharan, S., Mudzakir, A., Yoshinari, N., & Razali, M. R. (2023). A Symmetrical Tetra N-Heterocyclic Carbene Binuclear Silver(I) Complex: Synthesis, Characterization and Anticancer Study. Journal of Coordination Chemistry, 76(16-24), 1921-1940. https://doi.org/10.1080/00958972.2023.2289001
Praveen, P. A., & Babu, R. R. (2019). Evaluation of Nonlinear Optical Properties from Molecular Descriptors of Benzimidazole Metal Complexes by Principal Component Analysis. Journal of Molecular Graphics and Modelling, 93, 107447. https://doi.org/10.1016/j.jmgm.2019.107447
Arora, T., Devi, J., Dubey, A., Tufail, A., & Kumar, B. (2023). Spectroscopic Studies, Antimicrobial Activity, and Computational Investigations of Hydrazone Ligands Endowed Metal Chelates. Applied Organometallic Chemistry, 37(9), e7209. https://doi.org/10.1002/aoc.7209
Timoshnikov, V. A., Selyutina, O. Y., Polyakov, N. E., Didichenko, V., & Kontoghiorghes, G. J. (2022). Mechanistic Insights of Chelator Complexes with Essential Transition Metals: Antioxidant/Pro-oxidant Activity and Applications in Medicine. International Journal of Molecular Sciences, 23(3), 1247. https://doi.org/10.3390/ijms23031247
Abd El-Lateef, H. M., Khalaf, M. M., Kandeel, M., & Abdou, A. (2023). Synthesis, Characterization, DFT, Biological and Molecular Docking of Mixed Ligand Complexes of Ni(II), Co(II), and Cu(II) based on Ciprofloxacin and 2-(1H-benzimidazol-2-yl) phenol. Inorganic Chemistry Communications, 155, 111087. https://doi.org/10.1016/j.inoche.2023.111087
Fatima, T., Haque, R. A., Ahmad, A., Hassan, L. E. A., Ahamed, M. B. K., Majid, A. A., & Razali, M. R. (2020). Tri N-Heterocyclic Carbene Trinuclear Silver(I) Complexes: Synthesis and In-vitro Cytotoxicity Studies. Journal of Molecular Structure, 1222, 128890. https://doi.org/10.1016/j.molstruc.2020.128890
Lumivero (2024). XLSTAT Statistical and Data Analysis Solution. https://www.xlstat.com/en.
Nazri, M. Z., Zaini, N. S. M., Kamaruddin, N. N., Rameezal, R. N., Musa, N. F., Razali, M. R. & Basar, N. (2024). Synthesis, Characterizations and Multivariate Data Analysis of Non- and Nitrile-Functionalized Silver(I) and Palladium(II) N-Heterocyclic Carbene Complexes. Scientific Research Journal, 21(2), 89-117. https://doi.org/10.24191/srj.v21i2.26553
Sani, M. S. A., Ismail, A. M., Azid, A., Samsudin, M. S., & Yuswan, M. H. (2024). Incorporation of Partial Least Squares-Discriminant Analysis with Ultra-High-Performance Liquid Chromatography Diode-Array Detector for Authentication of Skin Gelatine Sources. Halalsphere, 4(1), 1-13. https://doi.org/10.31436/hs.v4i1.83
Nazri, M. Z., Cilwyn, B., Huda, K., Sreenivasan, S., & Razali, M. R. (2023). Synthesis, Structural and Anticancer Studies of Asymmetrical Dinuclear Silver (I) Di-N-heterocyclic Carbene Complexes. Malaysian Journal of Chemistry, 25(4), 207-221. https://doi.org/10.55373/mjchem.v25i4.207
Hussaini, S. Y., Haque, R. A., Haziz, U. F., Amirul, A. A., & Razali, M. R. (2021). Dinuclear Silver(I)- and Gold(I)-N-Heterocyclic Carbene Complexes of N-alkyl Substituted Bis-Benzimidazol-2-ylidenes with Aliphatic Spacer: Synthesis, Characterizations and Antibacterial Studies. Journal of Molecular Structure, 1246, 131187. https://doi.org/10.1016/j.molstruc.2021.131187
Nadeem, R. Y., Yaqoob, M., Yam, W., Haque, R. A., & Iqbal, M. A. (2022). Synthesis, characterization and biological evaluation of Bis-benzimidazolium salts and their silver(I)-N-heterocyclic carbene complexes. Medicinal Chemistry Research, 31(10), 1783-1791.https://doi.org/10.1007/s00044-022-02942-7
Hussaini, S. Y., Haque, R. A., Li, J. H., Zhan, S. Z., Tan, K. W., & Razali, M. R. (2019). Coinage Metal Complexes of N‐Heterocyclic Carbene Bearing Nitrile Functionalization: Synthesis and Photophysical Properties. Applied Organometallic Chemistry, 33(6), e4927. https://doi.org/10.1002/aoc.4927
Yeap, C. W., Haque, R. A., Yam, W. S., & Razali, M. R. (2019). The first Mesomorphic Benzimidazolium-based Silver(I)-N-Heterocyclic Dicarbene Complexes: Synthesis, Characterization and Phase Properties. Journal of Molecular Liquids, 277, 341-348. https://doi.org/10.1016/j.molliq.2018.12.075
Altuntaş, Ü., Güzel, İ., & Özçelik, B. (2023). Phenolic Constituents, Antioxidant and Antimicrobial Activity and Clustering Analysis of Propolis Samples based on PCA from Different Regions of Anatolia. Molecules, 28(3), 1121. https://doi.org/10.3390/molecules28031121
Jolliffe, I. T., & Cadima, J. (2016). Principal Component Analysis: A Review and Recent Developments. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 374(2065), 20150202. https://doi.org/10.1098/rsta.2015.0202
Bro, R., & Smilde, A. K. (2014). Principal component analysis. Analytical methods, 6(9), 2812-2831. https://doi.org/10.1039/C3AY41907J
Ibrahim, R. M., Eltanany, B. M., Pont, L., Benavente, F., ElBanna, S. A., & Otify, A. M. (2023). Unveiling the Functional Components and Antivirulence Activity of Mustard Leaves using an LC-MS/MS, Molecular Networking, and Multivariate Data Analysis Integrated Approach. Food Research International, 168, 112742. https://doi.org/10.1016/j.foodres.2023.112742
Wolczanski, P. T. (2024). Elemental Aspects of Transition Metals Pertinent to Organometallic Chemistry: Properties, Periodicity, Curiosities, and Related Main Group Issues. Organometallics, 43(8), 787-801. https://doi.org/10.1021/acs.organomet.3c00529
Ondar, E. E., Polynski, M. V., & Ananikov, V. P. (2023). Predicting 195Pt NMR Chemical Shifts in Water‐Soluble Inorganic/Organometallic Complexes with a Fast and Simple Protocol Combining Semiempirical Modeling and Machine Learning. ChemPhysChem, 24(11), e202200940. https://doi.org/10.1002/cphc.202200940
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2024 UNIMAS Publisher
This work is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International License.
Copyright Transfer Statement for Journal
1) In signing this statement, the author(s) grant UNIMAS Publisher an exclusive license to publish their original research papers. The author(s) also grant UNIMAS Publisher permission to reproduce, recreate, translate, extract or summarize, and to distribute and display in any forms, formats, and media. The author(s) can reuse their papers in their future printed work without first requiring permission from UNIMAS Publisher, provided that the author(s) acknowledge and reference publication in the Journal.
2) For open access articles, the author(s) agree that their articles published under UNIMAS Publisher are distributed under the terms of the CC-BY-NC-SA (Creative Commons Attribution-Non Commercial-Share Alike 4.0 International License) which permits unrestricted use, distribution, and reproduction in any medium, for non-commercial purposes, provided the original work of the author(s) is properly cited.
3) For subscription articles, the author(s) agree that UNIMAS Publisher holds copyright, or an exclusive license to publish. Readers or users may view, download, print, and copy the content, for academic purposes, subject to the following conditions of use: (a) any reuse of materials is subject to permission from UNIMAS Publisher; (b) archived materials may only be used for academic research; (c) archived materials may not be used for commercial purposes, which include but not limited to monetary compensation by means of sale, resale, license, transfer of copyright, loan, etc.; and (d) archived materials may not be re-published in any part, either in print or online.
4) The author(s) is/are responsible to ensure his or her or their submitted work is original and does not infringe any existing copyright, trademark, patent, statutory right, or propriety right of others. Corresponding author(s) has (have) obtained permission from all co-authors prior to submission to the journal. Upon submission of the manuscript, the author(s) agree that no similar work has been or will be submitted or published elsewhere in any language. If submitted manuscript includes materials from others, the authors have obtained the permission from the copyright owners.
5) In signing this statement, the author(s) declare(s) that the researches in which they have conducted are in compliance with the current laws of the respective country and UNIMAS Journal Publication Ethics Policy. Any experimentation or research involving human or the use of animal samples must obtain approval from Human or Animal Ethics Committee in their respective institutions. The author(s) agree and understand that UNIMAS Publisher is not responsible for any compensational claims or failure caused by the author(s) in fulfilling the above-mentioned requirements. The author(s) must accept the responsibility for releasing their materials upon request by Chief Editor or UNIMAS Publisher.
6) The author(s) should have participated sufficiently in the work and ensured the appropriateness of the content of the article. The author(s) should also agree that he or she has no commercial attachments (e.g. patent or license arrangement, equity interest, consultancies, etc.) that might pose any conflict of interest with the submitted manuscript. The author(s) also agree to make any relevant materials and data available upon request by the editor or UNIMAS Publisher.
To download Copyright Transfer Statement for Journal, click here