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Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.Nghiên cứu tổng hợp, cấu trúc và tính chất của một số phức chất cơ platinum(II) chứa isopropyl eugenoxyacetate.
MINISTRY OF EDUCATION AND TRAINING HA NOI NATIONAL UNIVERSITY OF EDUCATION - PHAM VAN THONG STUDY ON SYNTHESIS, STRUCTURE AND PROPERTIES OF SOME ORGANOPLATINUM(II) COMPLEXES BEARING ISOPROPYL EUGENOXYACETATE Specialized: Inorganic chemistry Code: 9.44.01.13 SUMMARY OF THESIS DOCTOR OF PHYLOSOPHY IN CHEMISTRY HANOI, 2023 The thesis has been completed at HANOI NATIONAL UNIVESITY OF EDUCATION Supervisor: Assoc Prof Dr Nguyen Thi Thanh Chi (Hanoi National University of Education) Assoc Prof Dr Huynh Han Vinh (National University of Singapore) Reviewer 1: Assoc Prof Dr Duong Ba Vu HCMC University of Education Reviewer 2: Assoc Prof Dr Nguyen Hung Huy VNU University of Science Reviewer 3: Assoc Prof Dr Le Thi Hong Hai Hanoi National University of Education The thesis will be defended in front of the University-level thesis evaluation committee at Hanoi National University of Education ……………… 2023 The thesis can be found at: National Library, Hanoi or Library of Hanoi National University of Education PUBLISHED IN THE THESIS CONTENT Pham Van Thong, Luc Van Meervelt, Nguyen Thi Thanh Chi* Cyclometalated platinum(II) complexes bearing natural arylolefin and quinolines ligands: Synthesis, characterizations, and in vitro cytotoxicity, Polyhedron, 228, 116160, (2022, Q2) Nguyen Thi Thanh Chi*, Pham Van Thong, Ngo Tuan Cuong, Luc Van Meervelt* Reaction pathways of the diplatinum complexes bearing a phenylpropene derived π/σ-chelator [Pt(µ-Cl)(arylolefin)]2 with weak/strong σ-donor neutral ligands, ChemistrySelect, (2022, Q2) (excepted) Pham Van Thong, Nguyen Thi Thanh Chi*, Mohammad Azam*, Cu Hong Hanh, Le Thi Hong Hai, Le Thi Duyen, Saud I Al-Resayes, Mahboob Alam, Nguyen Van Hai NMR investigations on a series of diplatinum(II) complexes possessing phenylpropenoids in CDCl3 and CD3CN: Crystal structure of a mononuclear platinum complex, Polyhedron, 115612, (2022, Q2) Nguyen Thi Thanh Chi*, Van Thong Pham, Han Vinh Huynh* Mixed Arylolefin/NHC Complexes of Platinum(II): Syntheses, Characterizations and In-Vitro Cytotoxicities, Organometallics, 39(19), 3505– 3513 (2020, Q1) Nguyen Thi Thanh Chi, Pham Van Thong and Luc Van Meervelt* Crystal structures of three platinacyclic complexes bearing isopropyl eugenoxyacetate and pyridine derivatives, Acta Cryst., E76, 1012–1017 (2020, Q3) Pham Van Thong, Nguyen Manh Thang, Nguyen Thi Thanh Chi* Study on the interaction between [Pt(µ-Cl)(isopropyl eugenoxyacetate-1H)]2 and 1,3-diisopropylbenzimidazolium bromide, V J Chem., 57(2), 218-224 (2019) Nguyen Thi Thanh Chi*, Pham Van Thong, Truong Thi Cam Mai, Luc Van Meervelt* Mixed natural arylolefin– quinoline platinum(II) complexes: synthesis, structural characterization and in vitro cytotoxicity studies, Acta Cryst., C74, 1732-1743 (2018, Q1) Han Vinh Huynh*, Van Thong Pham, Nguyen Thi Thanh Chi* Cyclometallated Platinum(II) Complexes with a Phenylpropene-derived π/σ-Chelator and N-heterocyclic Carbenes, Eur J Inorg Chem., 48, 56505655 (2017, Q1) Pham Van Thong, Nguyen Hien, Nguyen Son Ha, Nguyen Thi Thanh Chi* Synthesis and structure of some azolium salt, V J Chem., 55(2), 249-254 (2017) 10 Pham Van Thong, Truong Thi Cam Mai, Nguyen Thi Thanh Chi* The interaction between K[PtCl3(isopropyl eugenoxyacetate)] and two pyridine’s derivatives, Journal of Science of HNUE, 62, 18-25 (2017) 11 Chi Nguyen Thi Thanh, Thong Pham Van, Hai Le Thi Hong, Luc Van Meervelt* Crystallization experiments with the dinuclear chelate ring complex di-μ-chlorido-bis(η2-2-allyl-4-methoxy-5-{[(propan-2yloxy)carbonyl]methoxy}-phenyl-κC1)platinum(II), Acta Cryst., C72, 758-764 (2016, Q1) 12 Phạm Văn Thống, Nguyễn Thị Thanh Chi* Nghiên cứu tổng hợp cấu trúc hai phức chất K[PtCl3(isopropyl eugenoxyacetate)] [PtCl(isopropyl eugenoxyacxetate-1H)]2, Tạp chí Hóa học, 52(3), 381-386 (2014) OTHER RELATED PUBLICATIONS Pham Van Thong, Do Thi Thom, Nguyen Thi Thanh Chi* Synthesis and structure of two platinum(II) complexes bearing N-heterocyclic carbenes and dimethyl sulfoxide, V J Chem., 56(2), 146-151 (2018) Chi Nguyen Thi Thanh*, Mai Truong Thi Cam, Thong Pham Van, Long Nguyen, My Nguyen Ha, Luc Van Meervelt* Synthesis, structure and in vitro cytotoxicity of some platinum(II) complexes containing eugenol and 8-hydroxyquinoline-derived chelator, Acta Cryst., C73, 1030-1037 (2017) Phạm Văn Thống, Trương Thị Cẩm Mai, Bạch Thị Mãi, Nguyễn Thị Thanh Chi* Tổng hợp, cấu trúc, tính chất hai phức chất khép vịng platinum(II) chứa methyleugenol quinaldic acid, Tạp chí Hóa học, 54(5e1,2), 154-159 (2016) Phạm Văn Thống, Hồng Văn Trường, Lê Thị Duyên, Nguyễn Thị Thanh Chi* Phản ứng bất thường potasium tricloropiperidinplatinat(II) với para-nitroaniline, Tạp chí Hóa học, 53(3e12), 468-472 (2015) Chi Nguyen Thi Thanh, Truong Hoang Van, Thong Pham Van, Ngan Nguyen Bich and Luc Van Meervelt* Crystal structure of trans-dichlorido(4-nitroaniline-κN)(piperidine κN)platinum(II), Acta Cryst., E71, 644-646 (2015) Nguyễn Thị Thanh Chi*, Phạm Văn Thống, Trần Thị Đà Nghiên cứu tổng hợp, cấu trúc phức chất khép vòng platinum(II) chứa eugenoxyacetic acid, Tạp chí Hóa học, 52(5A), 319-323 (2014) Nguyễn Thị Thanh Chi*, Phạm Văn Thống Tổng hợp, cấu trúc hoạt tính kháng tế bào ung thư phức chất cis-[PtCl2(piperidine)(p-cloaniline)] cis-[PtCl2(piperidine)(xyclohexylamine)], Tạp chí Khoa học ĐHSPHN, 59(1), 156-161 (2014) 1 INTRODUCTION Reasons for choosing the topic The platinum(II) complexes have had an enormous role not only in theory but also in practical applications, especially in medical practices and in the organic synthesis industry In the medical field, there have been three generations of platinum complexes which are widely used in human cancer treatment in the names of Cisplatin, Carboplatin and Oxaliplatin However, due to their disadvantage of high toxicity and not responding to the rise of different types of cancer, research on synthesis of new platinum(II) complexes, especially complexes containing natural ligands, is attracting the attention of many domestic and foreign scientists In the chemical industry, catalysts are used to manufacture 80% of chemical products, particularly organometallic compounds for numerous processes Their importance is highlighted in Nobel prizes, such as Nobel Prize for organomagnesium compound of Grignard (1912); Nobel Prize for olefin metathesis with carbene organic catalyst by Y Chauvin , R H Schrock (2005); for palladium-catalyzed cross-coupling by Richard F Heck, Ei-ichi Negishi, Akira Suzuki (2010), etc Platinum is known to be a precursor that creates catalysts for many important metabolic processes such as hydrosilylation reactions, hydroaminations, C-C coupling reaction In those processes, platinum complexes act as active intermediates In Vietnam, research on organometallic platinum complexes has only started in the first decade of the 21st century, putting it two centuries behind research conducted elsewhere in the world However, the complex research group at Hanoi National University of Education has synthesized organoplatinum complexes with interesting structure Using simple and popular reagents, the authors have initiated a method for the synthesis of dinuclear chelate ring platinum complexes with general formula [Pt(μ-Cl)(arylolefin)]2, in which arylolefin is extracted or synthesized from vegetable essential oils such as safrole, methyleugenol, alkyl eugenoxyacetate These dinuclear complexes have been studied to interact with different amines to obtain mononuclear platinum complexes Most of the collected complexes that were tested for inhibitory activity of human cancer cells have demonstrated promising results (Fig 1) However, these complexes contain arylolefin ligand, which is isopropyl eugenoxyacetate This substance has not been used widely, and so far there has been no research on converting these dinuclear chilate ring complexes into new compounds for the purpose of creating catalysts Fig Synthesis of some platinum(II) bearing arylolefin complexes Continuing the research on the Pt(II) bearing arylolefin complexes in this topic, we chose the arylolefin isopropyl eugenoxyacetate - a derivative of eugenol (accounting for 70% in clove basil oil) as the research object for its applicability in medicine and organic synthesis catalysis In this study focus on the following tasks: - Synthesizing isopropyl eugenoxyacetate (iPrEugH) from clove basil oil and some azolium chloride salts from nitrogen heterocyclic azoles - From Pt and other chemicals, synthesizing complex K[PtCl3(iPrEugH)] (1) - From complex 1, synthesizing a dinuclear chelate ring complex containing iPrEug with the formula [Pt(μ-Cl)(iPrEug)]2 (2) and determining its structure by single crystal X-ray diffraction - Studying the interaction of complex with heterocyclic bidentate amines - Studying the interaction of complex with tricyclohexylphosphine and triphenylphosphine - Studying the interaction of complex with the synthesized azolium chloride salts to formPt(II) complexes containing simultaneously iPrEug and Nheterocyclic carbene (NHC) - Using chemical, physicochemical and physical methods to determine the composition and structure of the obtained complexes - Investigating the inhibitory activity on cancer cells of some complexes containing olefins and amines and initially studying the catalytic activities of some complexes for Sonogashira and hydrosilylation reactions New contributions of the thesis From mononuclear complex K[PtCl3(iPrEugH)] (1), a new dinuclear chelate complex of [Pt(μ-Cl)(iPrEug)]2 (2) has been synthesized, which is perceived as the crucial component leading to synthesis directions of other chelate organometallic compound of Pt(II) bearing iPrEug Three-dimensional structure of complex was determined and characterized using single crystal Xray diffraction (XRD), which is the basis for explaining other interesting results Efficient reacting conditions were found to prepare a series of new 20 mononuclear complexes containing iPrEug and coordinating sovent, amine, phosphine, or nitrogen heterocyclic carbene, including [PtX(iPrEug)L] (3–5, 10–14, 17–22); [Pt(iPrEug)L] (6–9); [PtCl(iPrEug)(PR3)] (15, 16), all of which come from dinuclear complex Structures of these complexes were determined through the combination of various up-to-date characterization techniques With detailed analysis on NMR and XRD results, not only their complicated structures were justified, but also some conclusions were drawn with predictive analytics on mechanisms of substitution reactions of dinuclear complexes [Pt(μCl)(arylolefin)]2 with other ligands In addition, the predictive analytics can help with determining the cis/trans configuration of the obtained products from these reactions The cytotoxicity test results of the four complexes containing amine groups on four human cancer cell lines have shown that complex 10 (very soluble in water) had inhibitory effects on the growth of all tested cell lines, with the obtained IC50 values ranging from 4.03–7.07 µM (which are greatly lower than those values of cisplatin) These data established the need to further investigate the complex 10 for its potential in biomedical applications The initial analysis on the catalytic activities of compounds 17–19 for the hydrosilylation reaction of silane derivatives and phenylacetylene showed that after hours of reacting at 700C, in the air, these compounds exhibited a great catalytic rate at 0.5 mol% The catalytic mechanism of 17–19 for these reactions was initially proposed This positive result has proven a promising application in the field of organic synthesis catalysis at industrial scale Layout of the thesis The thesis consists of three parts: the main content (113 pages), references (14 pages) and the appendix (102 pages) Specifically: - The main content of the thesis includes: pages of introduction, 24 overview pages, 16 experimental pages, 66 results and discussion pages, conclusion pages and pages of the author's portfolio This entire section has 54 pictures and 23 tables - References: 145 documents including 12 Vietnamese and 133 English documents - The appendix of the thesis includes: Spectrometer to determine the structural composition and attribution results of the studied compounds, results of resistance testing of cancer cells and catalyst test MAIN CONTENT OF THESIS CHAPTER OVERVIEW Overview of synthesis and properties of research ligands for complexation (alkyl eugenoxyacetate, phopshine and N-heterocyclic carbene - NHC, heterocyclic bidentate amines); research situation of platinum(II) complexes containing olefin, phosphine and NHC ligands; antitumor activity and catalytic activity of platinum(II) complexes CHAPTER EXPERIMENTAL 2.1 Chemicals, apparatus and research equipment 2.2 Synthesis of ligands 2.2.1 Synthesis of isopropyl eugenoxyacetate (iPrEugH) The iPrEugH ligand was synthesized by reaction of eugenoxyacetic acid with propan-2-ol for 18 hours at 100oC, using sulfuric acid as catalyst, the yield was 45% 2.2.2 Synthesis of azolium chloride salts The azolium chloride salts are synthesized by alkylation of imidazoles, benzimidazoles and triazoles with benzyl chloride or 2-bromopropane The reactions were carried out in CH3CN solvent at 80−85oC, after 48 hours, the products were obtained with a yield of 75−80% Fig 2.1 Diagram of the synthesis azolium chlorides 2.3 Synthesis of complexes The complexes were synthesized with the following procedure in Figure 2.2 Fig 2.2 Synthetic scheme of the examined complexes Where: - Sol (solvent): MeCN (3), Me2SO (4), Me2NCHO (5) - (N,OH): quinoline-8-ol (6), 2-methylquinoline-8-ol (7), 5,7dichloroquinoline-8-ol (8), quinoline-2-carboxylic acid (9) - Amine: 1,10-phenanthroline (10), 2,2’-bipyridine (11), 4,4’-dimethyl-2,2’bipyridine (12), 6,6’-dimethyl-2,2’-bipyridine (13) - PR3: tricyclohexylphosphine (14, 15), triphenylphosphine (16) NHC·HCl: 1,3-dibenzylimidazolium chloride (17) 1,3dibenzylbenzimidazolium chloride (18), 1,3-dibenzyl-1,2,4-triazolium chloride (19), 1-benzyl-3-isopropylbenzimidazolium chloride (20) - MX: LiBr (21), KI (22) 2.3.1 Synthesis of K[PtCl3(iPrEugH)] (1) The complex K[PtCl3(iPrEugH)] was synthesized from Zeise’s salt and i PrEugH with the yield of 95%according to the following reaction: K[PtCl3(C2H4)] + iPrEugH → K[PtCl3(iPrEugH)] + C2H4 2.3.2 Study on the synthesis of [Pt(μ-Cl)(iPrEug)]2 (2) The complex [Pt(μ-Cl)(iPrEug)]2 was synthesized from Zeise’s salt and i PrEugH with the yield of 70% in the solvent mixture of acetone-water (1 : 10, v/v) at 60 oC for 7hours The reaction equation is as indicated below: 2K[PtCl3(iPrEugH)] [Pt(μ-Cl)(iPrEug)]2 + 2KCl + 2HCl Producing a single crystals of the complex [Pt(μ-Cl)(iPrEug)]2 Solvent vapor diffusion method: In the solvent system of chloroform/diethyl ether or dichloromethane/diethyl ether, the greenish yellow needle crystals were obtained The product is complex Solvent evaporation method: In the solvents such as acetonitrile, dimethyl sulfoxide and dimethyl formamide, the obtained crystals are different from so these complexes are denoted as 3, and 2.3.3 Study on the interaction of [Pt(µ-Cl)(iPrEug)]2 with heterocyclic bidentate amines The complex reacts with amines with formula (N,OH) to form complexes 6-9 as the following equation: [Pt(μ-Cl)(iPrEug)]2 + 2(N,OH) → 2[Pt(iPrEug)(N,O)] + 2HCl While using the amine 1,10-phenalthroline and the derivative of 2,2'bipyridine, complexes 10–13 are obtained The reactions take place according to the equation: [Pt(μ-Cl)(iPrEug)]2 + amine → 2[PtCl(iPrEug)(amine)] The reactions were carried out in acetone or acetone/water solvents at room temperature Single crystals of complexes 7, 9–11, 13 were grown by solvent evaporation or solvent vapor diffusion 2.3.4 Study on the interaction of [Pt(µ-Cl)(iPrEug)]2 with derivatives of phosphine We changed a number of reaction conditions when studying the interaction of with phosphine derivatives, including solvent, conductive operation, and the : PR3 molar ratio The results show that the reaction can occur as the equation: [Pt(μ-Cl)(iPrEug)]2 + PR3 → 2[PtCl(iPrEug)(PR3)] [Pt(μ-Cl)(iPrEug)]2 + PR3 → 2[PtCl(iPrEug)(PR3)2] Through the purification process, three clean complexes, 14–16, are obtained with an efficiency of 90-93% Single crystals of 14 and 16 were grown by solvent evaporation 2.3.5 Study on the interaction of [Pt(μ-Cl)(iPrEug)]2 with azolium chloride salts The synthesis of 17–20 was carried out in acetone at room temperature in the presence of Ag2O or Na2CO3 After hours of reaction, the product was obtained with the yield of 85–90% The reaction takes place according to the equation: [Pt(μ-Cl)(iPrEug)]2 + 2(NHC·HCl)→ 2[PtCl(iPrEug)(NHC)] (17–20) Complexes 21 and 22 were synthesized according to the equation: [PtCl(iPrEug)(NHC)] + MX → [PtCl(iPrEug)(NHC)] Single crystals of 18, 20–22 were grown by solvent evaporation 2.4 STUDY ON THE COMPONENT AND STRUCTURE OF OBTAINED PRODUCTS 2.4.1 Study on the components Thin layer chromatography method The products were tested for purity by chromatography on silufol-UV thin plate, showing traces by UV lamp at the wavelength of 254nm at the Department of Chemistry, Hanoi National University of Education (HNUE) Determination of water of crystallization proportion and platinum The water of crystallization proportion and platinum of the complexes 1, 2, 14–16, 20 and 22 were determined by weight method at the Department of Chemistry, Faculty of Chemistry, HNUE Molecular electrical conductivity measurement Molecular electrical conductivity of 10–12 was measured on Conductivity Meter Hach - 88119 N at the Department of Chemistry, HNUE Atom technical analysis method Atom technical analysis of complexes 17–19 and 21 were measured on the Perkin-Elmer PE 2400 engine at the Department of Chemistry, National University of Singapore The ESI MS spectroscopy The ESI-MS spectrum was recorded on a 1100 LC-MSD-Trap-SL engine at Institute of Chemistry, Vietnam Academy of Science and Technology 2.4.2 Study on the structures Infrared spectroscopy (IR) The infrared spectrum was recorded on IMPACK-410 NICOLET spectrometer, at Institute of Chemistry, Vietnam Academy of Science and Technology and the Department of Chemistry, HNUE Nuclear magnetic resonance spectrocopy (NMR) Nuclear magnetic resonance spectrum of 1H NMR was recorded on Bruker AVANCE III (500 MHz) in suitable solvent at Institute of Chemistry, Vietnam National Academy of Science and Technology and the Department of Chemistry, VNU Hanoi-University of Science Single crystal X-ray diffraction method Single crystal X-ray diffraction of 2, 3, 7–10, 13, 14, 16, were measured on Bruker SMART 6000 at 100K at KU Leuven, Kingdom of Belgium, of 18, 19– 21 were measured on Bruker AXS SMART APEX at the Department of Chemistry, National University of Singapore 2.5 COMPLEXES BIOLOGICAL AND CATALYTIC ACTIVITIES EXAMINATION 2.5.1 Complexes anticancer activities examination The complexes 6, 7, 10, 11 and cisplatin were tested for the anticancer activity at Applied Biochemistry Department, Institute of Chemistry, Vietnam Academy of Science and Technology on human cancer cell lines: KB, HepG2, LU-1 and MCF7 2.5.2 Complexes catalytic activities examination The complexes 17–19 were tested for the catalytic activity for types of reactions: Sonogashira between phenylacetylene and 4-bromobenzaldehyde and hydrosilylation between derivatives of silane and phenylacetylene Catalytic activity of Sonogashira reaction examination A mixture of 4-bromobenzaldehyde (1.0 mmol), phenylacetylene (1.2 mmol) and 18 (5 mol%) in triethylamine (3 mL) was degassed by Ar followed by stirring at different temperatures and times After stopping the reaction, the mixture was added with water and was extracted with diethyl ether The removal of diethyl ether occcurred under reduced pressure to yield a white solid The product was measured and analysed 1H NMR spectra but no desired product was obtained Catalytic activity of hydrosilylation reaction examination 10 Fig 3.13 Diagram of synthesizing reaction of [PtCl(iPrEug)(solvent)] (3−5) 3.2 STUDY ON THE INTERACTION BETWEEN [Pt(μ-Cl)(iPrEug)]2 WITH BIDENTATE AMINES AND DETERMINATION OF COMPONENT AND STRUCTURE OF OBTAINED COMPLEXES 3.2.1 Study on the interaction between [Pt(μ-Cl)(iPrEug)]2 with bidentate amines When complex reacts with RQOH-type amines, we obtain neutral complexes 6−9 with high efficiency 85 ÷ 93%, the structure was shown in Fig 3.14 The obtained complexes is square planar, heteroatom N is at the cis position compared to the allyl group in the coordination sphere Fig 3.14 Synthesizing reaction equation of [Pt(iPrEug)(amine)] (6−9) With 1,10-phenalthroline and a derivative of bipyridine, when they react with at the molar ratio of 2: amine, which is 1: 2, we get product 10−13 with high efficiency (90 ÷ 95%) From the results of the molecular electrical conductivity measurement, the ESI-MS, IR and 1H NMR spectra, it can be predicted that they exist in ion structure A or neutral structure B as shown in Fig 3.15 Fig 3.15 The expected structure of 10−13 XRD results show that 10−13 has B structure, which means Pt(II) represents the coordinate number This is an abnormal phenomenon in the Pt(II) complex system containing arylolefin and amine The cause of this 11 phenomenon may be due to the presence of the σ, π-donor/π-acceptor bond and the chelate ring coordination of the strong ligand (N,N-chelate) as well as the phenyl group in 10 −13 3.2.2 Determination of component and structure of obtained complexes From the results of analysing ESI-MS, IR, 1H NMR and XRD spectra, the structure of complexes are determined and presented in Figures 3.15, 3.23, 3.24 and in the diagram in 3.14 Some data of ESI-MS, NMR and XRD spectra of complexes were listed in Table 3.5-3.9 Table 3.5 Some detected ions on ESI-MS spectra of 6−13, m/z (au), % Complex 10 11 12 13 [M + H]+ [M + H - C3H6]+ 603 (100) 561 (10) 617 (100) 574 (15) 671 (25) 596 (30) 631 (100) 589 (30) - [M + Cl]- [M - amine + 2Cl]637 (25) 529 (100) 650 (100) 529 (50) 706 (100) 529 (100) 666 (100) - [M - Cl]+ 638 (100) 614 (100) 642 (100) 642 (10) Table 3.6 1H NMR signals of iPrEug in and 6−13, (ppm), J (Hz) Complex* (c) H8a 2,59/2,57 d JPtH 110 (a) 2,85 d (a) 2,78 d (a) 2,70 ov (c) 10 (b) 11 (b) 12 (b) 13 (c) * 2,86 d JPtH 100 3,16 d JPtH 100 3,09 d JPtH 100 2,43 d JPtH 100 2,43 d JPtH 100 H8b H9 H10cis H10trans H3 H6 5,08 m 4,29/4,26 d 4,01 d 3,77 ov 6,57 s 6,40/6,38 s JPtH 70 2JPtH 70 JPtH 70 4,89 m 4,25 d 7,09 s 3,64 ov 3,68 d 6,73 s JPtH 60 2JPtH 60 JPtH 40 4,51 d 3,60 d 7,20 s 3,66 ov 5,08 m 6,74 s JPtH 60 JPtH 60 JPtH 40 4,87 m 4,22 d 3,69 d 6,98 s 3,53 dd 6,60 s 2 JPtH 70 JPtH 70 JPtH 70 JPtH 40 5,53 m 4,63 d 4,02 d 7,02 s 4,05 dd 6,68 s JPtH 60 2JPtH 60 JPtH 60 JPtH 40 5,99 m 4,69 d 4,41 d 6,93 s 4,04 dd 6,98 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 5,80 m 4,43 d 4,28 d 6,76 s 3,98 dd 6,93 s JPtH 70 2JPtH 60 JPtH 60 JPtH 40 5,77 m 4,40 d 4,24 d 6,76 s 3,58 dd 6,92 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 3,67 m 3,43 d 2,37 d 6,29 s 3,58 dd 6,60 s 2 JPtH 70 JPtH 60 JPtH 60 JPtH 40 solvent: (a): acetone-d6; (b): methanol-d4; (c): chloroform-d1 12 b) a) Fig 3.23 Structures of (a) and (b) were determined by XRD a) b) c) Fig 3.24 Structures of 10 (a), 11 (b) and 13 (c) were determined by XRD Table 3.8 Some bond length of complexes 7, 9−11 and 13 (Å) Data anti-2 10 11 13 Pt−C5 Pt−N Pt−C9 Pt−C10 Pt−O Pt−Cl 2,4773(7) 1,993(3) 2,108(3) 2,141(3) 2,3527(7) 1,997(3) 2,199(3) 2,136(4) 2,110(4) 2,008(2) 1,999(3) 2,212(3) 2,140(3) 2,128(3) 2,038(2) 2,142(4) 2,005(5) 2,105(6) 2,078(5) 2,5086(13) 2,148(4) 2,133(3) 2,008(3) 2,081(3) 2,091(3) 2,5277(8) 2,152(3) 2,206(3) 2,010(3) 2,070(4) 2,056(4) 2,4268(9) 2,212(3) C9−C10 1,393(5) 1,388(5) 1,400(5) 1,436(8) 1,422(5) 1,450(5) XRD results show that the length of the Pt−Cl bond in 10 and 11 (Table 3.8) is consistent with the assumption that this bond is splitted in aqueous solution to dissociate into two ions as well as their molecular electrical conductivity 3.3 STUDY ON THE INTERACTION OF [Pt(μ-Cl)(iPrEug)]2 WITH PHOSPHINE AND DETERMINATION OF COMPONENT AND STRUCTURE OF OBTAINED COMPLEXES 3.3.1 Study on the interaction of [Pt(μ-Cl)(iPrEug)]2 with phosphine 13 When complex reacts with PR3 (R: phenyl, cyclohexyl), PR3 not only splits the Pt–Cl bond, but also cuts the Pt–(C=C) bond depending on the ratio of the participants Experimental results show that the reaction between and phosphine derivatives occurs according to the diagram in Fig 3.25 Through the purification process, we have obtained clean complexes 14–16 with efficiency 90–93% Fig 3.25 Reaction between with derivatives of phosphine 3.3.2 Determination of the component and structure of obtained complexes The components and structure of 14–16 were determined by spectroscopic methods ESI-MS, IR, NMR and XRD (with 14 and 16) The results showed that the obtained complexes have structure as described in Fig 3.34 Tables 3.10 and 3.11 give some data on NMR and XRD of 14–16 Table 3.10 Some NMR signals of iPrEug in and 14–16, (ppm), J (Hz) Complex H8a H8b H9 H10cis 2,59/2,57 3,74-3,79 5,09 4,00 3,74 d 6,24 m 4,63/4,60 14 3,87 dd JPtH 100 JPtH 65 d 2JPtH 50 15 3,90 d 5,94 m 5,16 d 16 2,99 d 4,99 m 4,67 d C8 C9 38,2 91,2 14 41,1 121,83/121,75 H10trans 4,29/4,27 4,24/4,23 d JPtH 60 5,18 d 4,64 d C10 64,2 84,67/84,53 H3 6,57 H6 6,39 6,72 s 6,67 s JPtH 50 6,55 s 7,00 s 3JPtH 70 5,84 s 6,3 s 3JPtH 65 C5 141,1 129,45/129,4 Table 3.11 Values of some bond length (Å) and bond angle (0) of complexes 14 and 16 Data 14 16 14 16 Pt−C5 Pt−Cl Pt−P 2,033(11) 2,4773(7) 2,3527(7) 2,3059(7) 2,026(2) 2,3968(7) 2,3097(7) Cl−Pt−C5 Cl−Pt−P Cl−Pt−C9 168,1(3) 92,77(10) 87,4(4) 177,95(6) 91,88(2) 86,86(2) Pt−C9 2,230(11) Pt−C10 2,208(11) C9−C10 1,356(16) - - 1,299(3) C5−Pt−P P1−Pt−P2 C2C3PtP1 98,7(3) 89,46(6) 174,036(18) 93,50(15) 91,65(2) 14 a) b) Fig 3.34 Molecular models of 14 (a) and 16 (b) were determined by XRD 3.4 STUDY ON THE INTERACTION BETWEEN [Pt(μ-Cl)(iPrEug)]2 WITH AZOLIUM CHLORIDE SALTS 3.4.1 Study on the interaction between [Pt(μ-Cl)(iPrEug)]2 with azolium chloride salts Complexes 17–22 containing iPrEug and NHC were synthesized by the reaction of azolium chloride salt with complex in the presence of Ag2O or Na2CO3 with the yield of 85–90% The reaction happened according to the diagram in Fig 3.35 Complexes 20 and 21 were synthesized by the reaction of 18 with LiBr or KI according to the equation in Fig 3.35 with 95% efficiency Fig 3.35 Reaction diagram of with azolium salts with the presence of base Fig 3.36 Synthesizing reaction of 21 and 22 3.4.2 Determination of the component and structure of obtained complexes 15 From analysis results of elemental analysis, ESI-MS, IR, one-dimensional and two-dimensional NMR spectra, the structure of 17–22 is determined, in which iPrEug coordinates with Pt(II) through the C=C bond and the carbon atom of the benzene ring, the NHC ligand is at the trans position compared to the C=C bond (Fig 3.44) In particular, 17−22 are a very rare case of Pt(II) complexes containing three carbon complexing centers: aryl anion, neutral NHC and η2-olefin In addition, the rotational symmetry in solution of complexes 19 and 20 (Fig 3.39) is discovered due to the asymmetric NHC Tables 3.13–3.16 gives some data on MS, NMR and XRD spectra of 17–22 Table 3.13 Results of +MS spectra of 17–22, m/z (au), intensity (%) Complex i [PtCl( PrEug)(Bn2-imy)] (17) [PtCl(iPrEug)(Bn2-bimy)] (18) [PtCl(iPrEug)(Bn2-tazy)] (19) [PtCl(iPrEug)(iPr,Bn-bimy)] (20) [PtBr(iPrEug)(Bn2-bimy)] (21) [PtI(iPrEug)(Bn2-bimy)] (22) [M – X]+ 706 (100) 756 (100) 707 (100) 708 (100) 756 (100) 756 (100) [M + Na]+ 765 (8) 815 (24) 765 (88) 766 (24) 858 (30) 906 (62) Fig 3.39 Two rotational symmetries of complexes 19 and 20 Table 3.14.1H NMR signals of iPrEug in and 17–22a, (ppm), J (Hz) Complex H8a 2,59/2,57 3,05 d 17 JPtH 90 3,11 d 18 JPtH 90 3,10 d 19a JPtH 90 3,10 d 19b JPtH 90 3,09 d 20ab JPtH 90 3,14 d 20bb JPtH 90 3,13 d 21 JPtH 90 3,14 d 22 JPtH 90 * H8b 3,74-3,79 3,75-3,68 ov H9 H10trans H10cis 5,09 4,00 4,29/4,27 5,79 m 4,52 d 4,82 d 2 JPtH 65 JPtH 60 JPtH 50 5,92 m 4,67 d 4,95 d 3,75 dd JPtH 65 2JPtH 60 2JPtH 50 5,92 m 4,58 d 4,90 d 3,82 dd 2 JPtH 65 JPtH 60 JPtH 50 5,85 m 4,62 d 4,88 d 3,82 dd 2 JPtH 65 JPtH 60 JPtH 50 3,78-3,74 5,98 m 4,72 d 5,00 d ov JPtH 65 2JPtH 60 2JPtH 50 5,98 m 4,70 d 4,99 d 3,86 dd 2 JPtH 65 JPtH 60 JPtH 50 5,93 m 4,73 d 5,05 d 3,74 dd JPtH 65 2JPtH 60 2JPtH 50 5,98 m 4,83 t-d 5,18 d 3,73 dd 2 JPtH 65 JPtH 60 JPtH 50 solvent: (a): acetone-d6; (b): chloroform-d1 H3 6,57 6,70 s 6,72 s 6,73 s 6,73 s 6,64 s 6,65 s 6,74 s 6,78 s H6 6,39 5,57 s JPtH 65 5,78 s JPtH 65 5,37 s JPtH 65 5,45 s JPtH 65 6,08 s 5,66-5,63 ov 5,77 s JPtH 65 5,79 s JPtH 65 16 Table 3.15 Some 13C NMR signals of and 17–22, ppm Complex 17 18 19 20 21 22 C9 91,2 111,0 113,0 112,3 / 112,2 112,98 / 112,97 112,1 111,4 C10 64,2 84,1 86,4 85,4 / 85,1 86,3 / 85,9 85,4 83,9 C5 141,1 127,7 127,8 127,7 / 127,3 125,9 / 125,2 129,9 135,0 CNHC 172,9 184,2 177,0 181,8 / 181,7 184,3 184,5 Fig 3.44 Molecular models of 18 and 20–22 were determined by XRD Table 3.16 Some values of bond length (Å) and bond angle (0) of complexes 18 and 20–22 Phức chất Pt−CNCN Pt−C5 Pt−X Pt−C9 Pt−C10 C9−C10 X−Pt−C5 X−Pt−CNCN C5−Pt−CNCN PtC2X/NHC PtC2X/alkene 18 (X = Cl) 2,000(5) 1,997(5) 2,409(1) 2,219(5) 2,205(6) 1,378(8) 176,1(2) 91,2(2) 92,5(2) 70,2(2) 81,8(3) 20 (X = Cl) 1,996(6) 2,011(6) 2,401(2) 2,223(6) 2,207(7) 1,36(1) 175,2(2) 90,0(2) 92,5(2) 68,9(2) 79,3(3) 21 (X = Br) 2,006(5) 2,012(5) 2,5316(6) 2,222(5) 2,205(6) 1,372(8) 176,5(1) 90,6(1) 92,7(2) 70,5(1) 81,5(3) 22 (X = I) 2,002(2) 2,010(2) 2,7020(2) 2,227(2) 2,212(2) 1,376(3) 172,96(5) 92,19(5) 91,33(8) 72,80(5) 86,1(1) 17 3.5 SOME RESULTS FROM COMPARING THE STRUCTURE AND PROPERTIES OF ALL RESEARCH COMPLEXES By the reactions of complex with a number of reagents, 20 complexes have been synthesized and classified into groups I – V as shown in Fig 3.45 Group I includes 3–5 (convention is the cis configuration, which is structurally similar to the complexes [PtCl(arylolefin)(amine)]; Group II: 14 and 17–22 (convention is the trans configuration); Group III: 6–9; Group IV: 10–13; Group V: 15, 16 Fig 3.45 Structure of the researching complex groups 3.5.1 The relationship between the structure and spectral properties ESI-MS Complexes containing Pt−Cl bonds (except for group I) on +MS spectrum tend to form fragment ions corresponding to [M - Cl]+ cation NMR Spectrometry The results of structural studies of complexes 2–22 show that iPrEug can coordinate with Pt(II) in the following two ways: When coordinated with Pt(II) according to way A, the NMR signals of protons and carbon near the complexation center of iPrEug has the following characteristics: i) Protons H3 and H6 are singlets In the signal of H6 there is a satellite signal because of 195Pt split with 3JPtH = 40–65 Hz On the spectrum, no signal of the proton H5 is observed, and the 13C signal has a low intensity due to becoming a quaternary carbon ii) Two H8 protons are not equivalent giving two resonance spectra while in the resonant signal of H8a, the satellite signal caused by 195Pt splits with a very large spin-spin coupling constant of about 90–110 Hz iii) δ of H9, H10 tend to decrease compared to iPrEugH depending on the influence of other ligands in the coordination sphere and their spectra appeared 18 satellite signals 195Pt split with 2JPtH = 50–70 Hz δ of C9, C10 decreased sharply compared to that in free iPrEugH When only coordinating with Pt(II) through the C5 atom, type B, on the NMR spectrum of these complexes, only sign (i) is observed Table 3.17 Results of NMR spectrum of some complexes Pt(II)/olefin, δ (ppm), J (Hz) arylolefinH H9 5.90 – 5.97 H10cis 5.01 – 5.07 H10trans 5.04 – 5.08 C9 C10 H6 H8a 137.5 – 138.7 114.1 – 115.6 - Group I 4.14 – 5.08 JPtH 70 – 76 Hz 3.42 – 3.98 JPtH 70 – 78 Hz 3.47 – 4.02 JPtH 70 – 75 Hz 86.1 – 89.3 58.8 – 62.3 JPtH 35 – 45 Hz JPtH 102 – 110 Hz II 5.42 – 5.94 JPtH 65 Hz 3.80 – 4.73 JPtH 50 Hz 4.14 – 5.01 JPtH 60 – 65 Hz 110.7 – 113.8 79.0 – 85.4 JPtH 65 – 70 Hz JPtH 90 Hz L1: monodentate amine, acetonitrile, dimethyl sulfoxide, dimethylformamide L2: PR3, NHC Table 3.17 shows that: δ of H9, H10 in group II are larger than their δ in group I with an increase of about 0.7−1.5 ppm, especially the signal of H9 Similarly there is a sharp increase in δ of C9 and C10 with an amplitude of about 20−30 ppm when the cis configuration transforms to the trans configuration In addition, the 2JPtH, 3JPtH values for allyl protons in group I are larger than those in group II, particularly for H8a and H10cis with a difference between 12 - 28 Hz Meanwhile, the 3JPtH values of H6 in group II were 20 - 40 Hz larger than those in group I These results were explained by the stronger trans influence of the L2 ligand compared with the chlorido ligand in group II, in contrast, the trans effect of the L1 ligand is much stronger than that of the chlorido ligand in group I Thus, this NMR result can be used to distinguish the cis/trans configuration of the product when [Pt(μ-Cl)(arylolefin)]2 reacts with monodentate ligand Applying HEP (Huynh Electronic Parameter), if the trans position ligand is stronger donor, the capacity that the δ of C9 and C10 will be shifted towards the weak field is higher, that is to increase the olefinic properties of the C9−C10 bond or to weaken the Pt−(C=C) bond From the value of δ of C9 and C10 (Table 3.18), it can be seen that the ability to weaken the Pt−(C=C) bond of the 19 ligands tends to decrease in the order PCy3 > Bn2-bimy ≈ iPr,Bn -bimy > Bn2tazy > Bn2-imy > Cl- Table 3.18 Chemical shift of C9, C10 in some complexes, ppm Complex 14 18 20 19 17 C9 121,83/121,75 113,0 112,98 / 112,97 112,3 / 112,2 111,0 91,2 C10 84,67/84,53 86,4 86,3 / 85,9 85,4 / 85,1 84,1 64,2 The results of XRD of single crystals The results in Table 3.19 show a significant increase in the bond length Pt−C9, Pt−C10 as well as the decrease of the bond length C9−C10 when complex transforms to group IV complexes, which indicates that Pt−(C=C) is weakened while increasing the olefinic properties of C=C Compared with group I (containing amine ligand or solvent), group IV complexes containing stronger electron donor ligands tend to make the Pt−(C=C) weaker, consistent with the observation on NMR spectrum With complex groups II and III containing chelating ring amine, because Pt(II) changed the coordinate number from to 5, the length of these bonds in these two complex groups changed significantly Table 3.19 Bond length Pt−C9, Pt−C10 and C9−C10 at some complexes, Å Complex Pt−C9 Pt−C10 C9−C10 I II III IV 2,131−2,134 2,136−2,140 2,07−2,105 2,219−2,230 2,118−2,131 2,10−2,138 2,056−2,091 2,205−2,208 1,388−1.401 1,388−1,40 1,422−1,450 1,356−1,378 2,108 2,141 1,393 3.5.2 Reaction direction of [Pt(μ-Cl)(iPrEug)]2 with σ donor ligand Research results on the interaction between complex [Pt(μ-Cl)(arylolefin)]2 with L1 ligands (moderate/weak σ donor ligand) or L2 ligands (strong σ donor ligand) in different conditions only form the product [PtCl(arylolefin)(L1)] (group I) or [PtCl (arylolefin)(L2)] (group II) respectively (Figure 3.47) Thus, it can be concluded that the determining factor for the formation of group I or group II products is not the reaction conditions, but rather the nature of the reactants, including steric factors and electronic properties (rearrangment degree, T, transphobia) The selective formation of group II products when dimer complexes interact with the L2 ligand is determined by an electronic factor, which means T(Caryl/L2) > T(Caryl/Cl) Meanwhile, the steric factor determines the reaction direction to form the selective products of group I with the L1 ligand at the cis position compared with the C=C group (Fig 3.47) The reason may the insignificant difference between T(Caryl/L1) and T(Caryl/Cl), where by the displacement effect 20 of the Caryl/Cl pair is not small enough to compensate for the repulsion between the hard benzene ring of arylolefin and L1 Fig 3.47 Reaction of and [Pt(μ-Cl)(arylolefin)]2 with σ donor ligand For heterocyclic bidentate amines, the results showed that when amines belong to the N−OH group, they tend to separate H atoms of the OH group to form chelate ring coordination with Pt(II) through N and O atoms (Fig 3.47) The obtained complex has a square planar structure and N heterotroatom has priority to occupy the cis position in comparison with the C=C bond For amine containing N heteroatoms, it is possible to form chelate ring coordination with Pt(II) creating pentadentate complexes of group III with square pyramidal and trigonal bipyramid structure Fig 3.48 Reaction of with heterocyclic bidentate amines 3.6 ANTICANCER ACTIVITIES AND CATALYTIC ACTIVITIES OF SOME COMPLEXES 3.6.1 Complexes anticancer activities examination The results of investigating the inhibitory activity of human cancer cells of complexes 6, 7, 10 and 11 showed that 10 (good solubility in water) has the ability to inhibit all four tested cell lines, including epithelium cancer (KB), liver cancer (Hep-G2), lung cancer (LU-1) and breast cancer (MCF-7) with an IC50 value of 4.03−7.07 µM, much lower than cisplatin (Table 3.20) This result shows that 10 is worth continuing to be researched for the purpose of medical application In addition, the results shows that the activity of containing i PrEug in a chelate ring coordination with Pt(II) via the carbon atom of the benzene ring and C=C decreased 9−80 times compared to the complex [PtCl(iPrEug)(QO)], where iPrEugH coordinates only with Pt(II) through C=C 21 Table 3.20 IC50 values of the studied complexes and some other compounds, (µM) Complex [Pt( PrEug)(QO)] (6) [Pt(iPrEug)(MeQO)] (7) [PtCl(iPrEug)(Phen)] (10) [PtCl(iPrEug)(Bpy)] (11) Ellipcitine Cisplatin Other PtII complex Q-OH Phen i KB 4,05 18,43 5,19 19,32 1,26 15,2 6,0−22,5 37,89 - LU-1 27,90 85,89 4,03 > 38,52 1,42 42,9 62,96 - Hep-G2 26,34 67,79 7,07 20,82 2,15 13,3 3,4−14,4 43,54 - MCF-7 48,80 31,75 5,69 > 38,52 1,83 45,7 4,6−16,8 40,37 26,28 3.6.2 Complexes catalytic activities examination After synthesizing 17–22, three complexes [PtCl(iPrEug)(Bn2-imy)] (17), [PtCl(iPrEug)(Bn2-bimy)] (18), and [PtCl(iPrEug)(Bn2-imy)] (19), the halogen, olefin and benzyl-branched at NHC ligands are fixed in complexes, only change the selected NHC to test the catalytic activity as well as structural effects on catalytic activity of these complexes First, we proceed to catalyze the Sonogashira reaction between phenylacetylene and 4-bromobenzaldehyde The results show that complex 18 was not able to catalyze this reaction The results are not as expected, it also shows that the catalytic study on Pt(II) containing arylolefin and NHC for Sonogashira reaction should not be promoted Next, the hydrosilylation reaction between triethylsilane and phenylacetylene is selected to evaluate the catalytic activity of 17–19 Table 3.22 Research results on the catalytic activity of 17–19 for the reaction between triethylsilane and phenylacetylene α No Catalyst mol% 18 2 18 18 0,5 17 0,5 19 0,5 17 0,1 18 0,1 19 0,1 Time 2 2 2 Temperature 70 70 70 70 70 70 70 70 β(E) Yield > 99% > 99% > 99% > 99% > 99% 90% 57% 96% %α 18 20 18 20 20 24 25 23 %β(E) 82 80 82 80 80 76 75 77 22 Table 3.23 Effect of complex 18 on the hydrosilylation of PhCCH/MePhCCH with silane derivatives No R1 R2 R3 Et Et Et Me Me Ph Ph Ph Ph Me Me3SiO Me3SiO EtO EtO EtO Et Et Et Me Me Ph Ph Ph Ph Me Me3SiO Me3SiO 10 EtO EtO EtO R H H H H H Me Me Me Me Me Yield (%) 100 100 100 100 100 100 100 100 100 100 %α 18 26 13 30 35 18 20 28 33 %β(E) 82 74 87 70 65 82 80 93 72 67 Experimental results (Table 3.22, 3.23) are very optimistic when complexes 17–19 catalyze the hydrosilylation reaction between silane derivatives and phenylacetylene 0.5 mol% catalyst at mild conditions (70oC, hours reaction in air and without using solvents) In addition, the results also show that the azole structure of NHC is one of the important factors affecting the catalytic activity for the hydrosilylation reaction of the Pt(II)/arylolefin/NHC complex Therefore, this is necessary to carry out further research with other NHC, examine their effect and look for indicators that help predict complexes with good catalytic activity In comparison with some other Pt(II) complexes containing NHC, it showed that 17–19 had better activity both in terms of metabolism and selectivity under much milder conditions This illustrates the important role of the cyclic arylolefin ligand in 17–19 to the metabolism and selectivity of this reaction Based on the mechanism of Chalk–Harrod, we initially propose a catalytic mechanism for the hydrosilylation reaction by 17−19 through phases as shown in Figure 3.54 In order to understand deeply the catalytic mechanism of 17−19 for this reaction, further experimental and computational studies are needed However, this initial success will open up a research direction for natural-derived arylolefin Pt(II) complexes and NHC in the catalytic field There is a need to further study the applications of potential compounds similar to 17−19 in the near future 23 Fig 3.54 Proposed mechanism for hydrosilylation reaction catalyzed by 17−19 CONCLUDE The complex K[PtCl3(iPrEugH)] (1) was synthesized with a high efficiency of 95% using clove basil essential oil, Pt, and necessary chemicals By alkylation of azoles, azolium chloride salts (NHC·HCl) were synthesized, which are precursors to synthesize NHC-containing Pt(II) complexes From 1, a new dinuclear complex [Pt(μ-Cl)(iPrEug)]2 (2) has been synthesized, the growing process the single crystal of shows that this complex is very reactive with solvents such as CH3CN, DMSO, DMF to form mononuclear complexes with the formula [PtCl(iPrEug)(solvent)] (3−5, group I) By the reaction of with heterocyclic bidentate amines, phosphine derivatives and NHC·HCl salts as well as ligand transformation in the coordination sphere, 17 complexes have been synthesized with high efficiency (85-95%) include: Group Molecular formula L/complex PCy3/14, Bn2-imy/17, Bn2-bimy/18, Bn2-tazy/19, i II [PtCl( PrEug)(L)] iPr,Bn-bimy/20; [PtBr(iPrEug)(Bn2-bimy)] (21), [PtI(iPrEug)(Bn2-bimy)] (22) III [Pt(iPrEug)(L)] QO/6, MeQO/7, ClQO/8, QCOO/9 i IV [PtCl( PrEug)(L)] Phen/10; Bpy/11; 4-MeBpy/12; 6-MeBpy/13 V [PtCl(iPrEug)(L)2] PCy3/15, PPh3/16 In which, 17−22 is a very rare case of Pt(II) complexes containing carbon complexation centers: aryl anion, neutral NHC and η2-olefin Using a combination of Pt and water of crystallization proportion, elemental analysis, EDX, ESI-MS, IR, 1D and 2D NMR spectroscopy, especially X-ray diffraction method for 13/22 complexes, the structure of 22 new complexes 1−22 have been determined 24 By detailed analysis of the X-ray diffraction and spectra, many subtleties have been drawn in the structure of the 22 complexes: - In complexes 2−14 and 17−22, iPrEug cyclic coordination with Pt(II) via C=Callyl and C5 atom of the benzene ring While in 15, 16 iPrEug only coordinates with Pt(II) through C5 and in iPrEugH is not deprotonated and coordinates with Pt(II) via C=Callyl - In group I, the ligands CH3CN, DMSO and DMF coordinate with Pt(II) through N, S and O atoms, respectively In group II, PCy3 and NHC coordinate with Pt(II) through P and CNHC and occupy the trans position compared to C=Callyl In group III, the amines are deprotonated in the OH group and form chelate ring coordination with Pt(II) through both N and O The solvent ligand or the N heterodimer of the amine is in the cis position relative to C=Callyl The amines in group IV are cyclically coordinated with Pt(II) via both two N atoms The two PR3 ligands in group V make the bond with Pt(II) via the P atom and in the trans position in the coordination sphere - Complexes in groups I, II, III and V have square planar structure, Pt(II) in group IV have pentadentate coordination with square pyramidal (10, 11) and trigonal bipyramid structure (13) - Comparing the relationship between the structure and properties of the I-V complex groups has drawn some normative conclusions: (1) When interacting with to form a mononuclear complex [PtCl(arylolefin)(L1/L2)], the strong electron donor L2 will occupy the trans position to C=Callyl due to being dominated by the electronic factor, while the medium/weak electron donor ligand will occupy the cis position due to the orientation of the steric factors but not influenced by reaction conditions; (2) The introduction of strong electron donor ligands such as PR3, NHC weakened the Pt–(C=Callyl) bond compared with that in complex The results of the investigation of the inhibitory activity of human cancer cells of the complexes 6, 7, 10 and 11 showed that 10 (well soluble in water) was able to inhibit all tested cell lines, including: KB, HepG2, Lu and MCF7 with IC50 values of 4.03–7.07 µM, much lower than cisplatin This result shows that 10 is worthy for further research with the aim of applying in medicine The results of study on catalytic activity of 17–19 for the hydrosilylation reaction between silane and phenylacetylene derivatives showed that, after hours of reaction at 70oC in the air, 17−19 catalyzes the this reaction very well at 0.5 mol% catalyst The catalytic mechanism of 17–19 was initially proposed for these reactions This is a promising result for application in the field of organic synthesis catalysts on the industrial scale