Efficient anf reusable ni based metal organic framework catalyzed carboxylation of halides with co2

16 Scheme 1.3: The synthesis of phenylacetic acids under rhodium-catalyzed carbonylation conditions [7].. 27 Scheme 1.12: The cross-coupling reaction of phenylacetylene and phenylboronic

VIETNAM NATIONAL UNIVERSITY HOCHIMINH CITY

HCM City University of Technology

MINH-DUNG TRAN

Chuyên ngành: Kỹ thuật Hóa học

Mã ngành: 60 52 03 01

Ho Chi Minh City, July , 2016

EFFICIENT AND REUSABLE Ni-BASED-METAL ORGANIC FRAMEWORK CATALYZED CARBOXYLATION OF HALIDES WITH CO2

CÔNG TRÌNH ĐƯỢC HOÀN THÀNH TẠI TRƯỜNG ĐẠI HỌC BÁCH KHOA –ĐHQG -HCM

Cán bộ hướng dẫn khoa học :

(Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ chấm nhận xét 1 :

(Ghi rõ họ, tên, học hàm, học vị và chữ ký) Cán bộ chấm nhận xét 2 :

(Ghi rõ họ, tên, học hàm, học vị và chữ ký) Luận văn thạc sĩ được bảo vệ tại Trường Đại học Bách Khoa, ĐHQG Tp HCM ngày tháng năm

Thành phần Hội đồng đánh giá luận văn thạc sĩ gồm: (Ghi rõ họ, tên, học hàm, học vị của Hội đồng chấm bảo vệ luận văn thạc sĩ) 1

2

3

4

5

Xác nhận của Chủ tịch Hội đồng đánh giá LV và Trưởng Khoa quản lý chuyên ngành sau khi luận văn đã được sửa chữa (nếu có) CHỦ TỊCH HỘI ĐỒNG TRƯỞNG KHOA…………

ĐẠI HỌC QUỐC GIA TP.HCM

TRƯỜNG ĐẠI HỌC BÁCH KHOA

CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM

Độc lập - Tự do - Hạnh phúc

NHIỆM VỤ LUẬN VĂN THẠC SĨ

Họ tên học viên: Trần Minh Dũng

Ngày, tháng, năm sinh: 18-11-1991

Chuyên ngành: Kỹ Thuật Hóa Học

MSHV: 13051165

Nơi sinh: Tây Ninh

Mã số : 60.52.03.01

I TÊN ĐỀ TÀI: Efficient and reusable Ni-based-metal organic framework

catalyzed carboxylation of halides with CO 2

II NHIỆM VỤ VÀ NỘI DUNG:

• Tổng hợp và khảo sát cấu trúc vật liệu MOF Ni2(BDC)2(DABCO)

• Khảo sát tối ưu phản ứng carboxylation benzyl bromide

III NGÀY GIAO NHIỆM VỤ : (Ghi theo trong QĐ giao đề tài): 19/01/2015

IV NGÀY HOÀN THÀNH NHIỆM VỤ: (Ghi theo trong QĐ giao đề tài): 17/06/2016

V CÁN BỘ HƯỚNG DẪN (Ghi rõ học hàm, học vị, họ, tên) :

Acknowledgement

A completed study would not be done without any assistance Therefore, I conducted this research gratefully gives acknowledgement to their support and motivation during the time of doing this research as a requirement of completing Master of Science Thesis

First of all, I would like to express my endless thanks and gratefulness to

my supervisor Dr Truong Vu Thanh, Prof Phan Thanh Son Nam and Tran Duc Thien Their kindly support and continuous advice went through the process of completion of my thesis Their encouragement and comments had significantly enriched and improved my work Without their motivation and instructions, the thesis would have been impossible to be done effectively: So far, I would like to thanks to groups who took charge in the process of data collection and data entry for doing this research as a part of the project.I would like to state my thanks to Bach Khoa University where supported financial for the project and provided me scholarship to pursuing and completing my degree.My special thanks approve to

my parents for their endless love, care and have most assistances and motivation

me for the whole of my life As last, my deeply thanks come to all my friends during time I study in Bach Khoa University

Ho Chi Minh City, July , 2016

Trần Minh Dũng

ABSTRACT

The utilization of linker Benzen-1,4-dicarboxylic acid (H2BDC) and ligand diazabicyclo(2.2.2) octane (DABCO) for the synthesis of Ni2(BDC)2(DABCO) was implemented by solvothermal method The structure of this materials were characterized by using several various techniques, including X-ray powder

1,4-diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma (ICP) analysis, and

nitrogen physisorption measurements

The Ni2(BDC)2(DABCO) was used as heterogeneous catalysts for the direct carboxylation of benzyl bromide with CO2 Several essential factors including solvent, temperature, catalyst amount, type of catalysts and the amount of reductant were investigated In leaching test, the catalyst was facilely separated from the reaction by centrifugation The catalyst recyclability was also specifically examined and the reaction could be reused several times without a significant degradation in catalytic activity The products were confirmed by

1H NMR and 13C NMR To the best of our knowledge, there are no previous reports on carboxylation of halides using CO2 under MOFs catalysis

LỜI CAM ĐOAN

Tôi xin cam đoan rằng:

Số liệu trong luận văn hoàn toàn do tôi thực hiện và chưa từng được sử dụng trong các bài báo, công trình nào khác

Mọi sự giúp đỡ cho việc thực hiện luận văn này đã được cảm ơn và thông tin trích dẫn đều có nguồn gốc rõ ràng

Tác giả luận văn

NMR: Nuclear magnetic resonance

XRPD: X-ray Powder Diffraction

H2DBC: Bezene-1,4-dicarboxylic acid

DABCO: 1,4-diazabicyclo(2.2.2) octane

SEM: Scanning electron microscopy

TEM: Transmission electron microscopy

TGA: Thermogravimetric analysis

ICP: Inductively coupled plasma

EtOAc: Etyl acetat

List of Tables

Table 2.1: List of chemicals needed for synthesizing Ni2(BDC)2(DABCO) 34Table 2.2 List of purification chemical 36Table 2.3 The different amount of phenylacetic acid used for the standard line graph 38Table 3.1 The effect of several type catalyst on reaction yield 51Table 3.2 The effect of the amount MgCl2 on yield reaction 53Table 3.3 The effect of different solvents on reaction conversion and yield 54

List of Schemes

Sheme 1.1: Synthesis of phenylacetic acids via Willgerodt-Kindler reaction [5] 15

Scheme 1.2: The synthesis of phenylacetic acid in the carbonylation reaction [6] 16

Scheme 1.3: The synthesis of phenylacetic acids under rhodium-catalyzed carbonylation conditions [7] 16

Scheme 1.4: Ni-Catalyzed Carboxylation of Alkyl Bromides [8] 17

Scheme 1.5: Ni-catalyzed reductive carboxylation of Allyl Esters with CO2 [9] 17

Scheme 1.6: Ni-Catalyzed Carboxylation of C(sp2) − and C(sp3)−O Bonds with CO2 [10] 17

Scheme 1.7: Ni-Catalyzed Carboxylation of alkyl halides with CO2 [11] 18

Scheme 1.8 Ni-MOF carboxylation of benzyl halides 18

Scheme 1.9: The hydrogenation with catalytic nickel nanoparticles embedded in MOF-1 [44] 26

Scheme 1.10: The hydrogenation with Nickel nanoparticles supported on MOF-5 [45] 26 Scheme 1.11:The arylation of aldehydes with arylboronic acids using Ni(HBTC)(BPY) catalyst [46] 27

Scheme 1.12: The cross-coupling reaction of phenylacetylene and phenylboronic acids using the Ni2(BDC)2(DABCO) as catalyst [50] 27

Scheme 1.13: The direct heterocycle C–H arylation reactions between azoles and arylboronic acids using Ni2(BDC)2(DABCO) as a catalyst [51] 27

Scheme 1.14 Nickel-catalyzed double carboxylation of various internal alkynes 28

Scheme 1.15 Synthesis of phenylacetic acids 30

Scheme 1.16 Carboxylation of secondary and tertiary alkyl halides 30

Scheme 1.17 Mechanistic experiments 31

Scheme 1.18 Optimization of the Reaction Conditions 31

Scheme 1.19 Nickel-catalyzed carboxylation of vinyl chlorides 32

Scheme 2.1 Ni-MOF carboxylation of benzyl bromide 37

List of Figures

Figure 1.1: Significance of Phenylacetic Acids [2] 14

Figure 1.2: Structure of Plavix (Clopidogrel) 15

Figure 1.3: Number of publications on MOFs over the past decade 19

Figure 1.4: General structure of MOFs [13] 19

Figure 1.5: Some different MOFs’ structures [14] 20

Figure 1.6: Aromatic dicarboxylates varying in length used as linkers [13] 20

Figure 1.7: Possible applications of MOFs in various areas [13] 23

Figure 1.8: The ability of MOF adsorption as compared to the traditional adsorption [35] 23

Figure 1.9 : Gravimetric uptake curves of CH4, CO2, H2 and N2 on SIFSIX-3-Zn MOF [37] 24

Figure 1.10 Examples of chemical fixation of CO2 [52] 29

Figure 1.11 Ni-Based MetalOrganic Frameworks Containing Paddle-Wheel Type Inorganic Building Units via High-Throughput Methods [33] 33

Figure 2.1: Structure simulation of Ni2(BDC)2(DABCO) [57] 35

Figure 3.1 X-ray powder diffractograms of MOF Ni2(BDC)2(DABCO) 41

Figure 3.2 FT-IR spectra of Ni2(BDC)2(DABCO) 42

Figure 3.3 SEM micrograph of Ni2(BDC)2(DABCO) 43

Figure 3.4 TEM micrograph of the Ni2(BDC)2(DABCO) 43

Figure 3.5 TGA of Ni2(BDC)2(DABCO) 44

Figure 3.6 Nitrogen adsorption/desorption isotherm of the Ni2(BDC)2(DABCO) 45

Figure 3.7 Pore size distribution of the Ni2(BDC)2(DABCO) 46

Figure 3.8 The standard line graph of phenyacetic acid 47

Figure 3.9 The effect of room temperature on conversion and GC yield 48

Figure 3.10 The reaction rate at 40OC 49

Figure3.11 The reaction at 60oC 49

Figure 3.12 The effect of catalyst loading on carboxylation reaction conversion and yield 50

Figure 3.13 The effect of the amount of reductant on the reaction conversion and yield 52

Figure 3.14 Leaching test indicated no contribution from homogeneous catalysis of active species leaching into reaction solution 55

Figure 3.15 Comparing reusability of catalyst 56

Figure 3.16 XRD of the resused Ni2(BDC)2(DABCO) 57

ABSTRACT 1

LIST OF ABBREVIATIONS 6

CHAPTER 1: LITERATURE REVIEW 14

1.1 The Synthesis of Phenyacetic Acids 14

1.1.1 The importance of phenylacetic acids 14

1.1.2 Conventional synthesis of phenylacetic acids 15

1.2 Our approach 17

1.3 Metal- Organic Frameworks 18

1.3.1 Introduction 18

1.3.2 Structure 19

1.3.3 Synthetic methods of MOFs 21

1.3.4 Properties 21

1.3.5 Application of MOFs 23

1.4 Potential of Nickel- MOFs in Catalysis 25

1.5 Nickel-catalyzed carboxylation of Aromatic Compounds with Carbon Dioxide 28

1.6 The Metal –Organic Framework Ni2(BDC)2(DABCO) 32

CHAPTER 2: EXPERIMENTALS 34

2.1 The Metal-Organic Framework Ni2(BDC)2(DABCO) 34

2.1.1 Materials and instrumentation 34

2.1.2 Synthesis of Ni2(BDC)2(DABCO) 35

2.2 The Direct Carboxylation of Akyl Halide with CO2 36

2.2.1 Materials and instrumentation 36

2.2.3 Leaching test and the reusability of catalyst: 39

CHAPTER III: RESULTS AND DISCUSSION 41

3.1 Characterization of Ni2(BDC)2(DABCO) 41

3.1.1 XRD result of Ni2(BDC)2(DABCO) 41

3.1.2 FT-IR results of Ni2(BDC)2(DABCO) 41

3.1.3 SEM and TEM results of Ni2(BDC)2(DABCO) 42

3.1.4 TGA results of Ni2(BDC)2(DABCO) 43

3.1.5 Nitrogen physisorption measurements of Ni2(BDC)2(DABCO) 44

3.1.6 ICP result of Ni2(BDC)2(DABCO) 46

3.2 The Carboxylation of Benzylbromide with CO2 46

3.2.1 The standard line graph of phenyacetic acid 47

3.2.2 The influence of temperature 47

3.2.3 The influence of catalyst loading 50

3.2.4 The influence of several kind of catalyst 51

3.2.5 The influence of the amount of reductant 52

3.2.6 The influence of the amount of additive material 53

3.2.7 The influence solvent 53

3.2.8 The leaching test study 54

3.2.9 The catalyst recycling 56

CHAPTER IV:CONCLUSION 58

REFERENCE 59

APPENDICES 64

CHAPTER 1: LITERATURE REVIEW

1.1 The Synthesis of Phenyacetic Acids

1.1.1 The importance of phenylacetic acids

Phenylacetic acid is one of the most important organic chemical materials, widely used in the field of medicine, pesticide, aromatizer and so on In more details, the interest in these compounds arises from the fact that a large number

of complex molecules such as vancomycin, carbenicillin, ibuprofen, diclofenac, lyrica or lipitor, among many other displayed significant biological activities [1] Especially, lipitor is ranked the first in the top 200 pharmaceutical Products

by Worldwide Sales in 2009 [2]

Figure 1.1: Significance of Phenylacetic Acids [2]

Besides, phenylacetic acids are used as intermediates in synthesis of some outstanding drugs, for instance, Plavix is a potent anti- platelet drug launched in

1997 by Sanofi- Synthelabo [3,4]

Figure 1.2: Structure of Plavix (Clopidogrel)

1.1.2 Conventional synthesis of phenylacetic acids

According to M Mujahid Alam and his partners’ study, phenylacetic acids were synthesized by Willgerodt-Kindler reaction under PTC (Phase Transfer Catalytic) condition [5]

Sheme 1.1: Synthesis of phenylacetic acids via Willgerodt-Kindler reaction [5]

Other studies concentrated on the carbonylation of alkyl halides For example, ZuminQiu and co-workers set a carbonylation reaction under milder condition

Scheme 1.2: The synthesis of phenylacetic acid in the carbonylation reaction [6]

Furthermore, the direct formation of carboxylic acids under a rhodium catalyst was studied in Department of medicinal chemistry in Canada by Andre´ Giroux and co-workers [7]

Scheme 1.3: The synthesis of phenylacetic acids under rhodium-catalyzed carbonylation

conditions [7]

However, the studies above still presented various limitations such as long reaction times, hazardous reaction conditions and difficulty in product isolation and purification Therefore, there was an intense demand to develop a new and efficient method for the synthesis of biologically active phenylacetic acids under mild and ecofriendly reaction conditions As a result, a series of studies

of carboxylation using CO2 as an inexpensive and environmental-friendly chemical reagent has published by Ruben Martin

Scheme 1.4: Ni-Catalyzed Carboxylation of Alkyl Bromides [8]

Scheme 1.5: Ni-catalyzed reductive carboxylation of Allyl Esters with CO 2 [9]

Scheme 1.6: Ni-Catalyzed Carboxylation of C(sp 2 ) − and C(sp 3 )−O Bonds with CO 2 [10]

1.2 Our approach

The carboxylation of alkyl halides with CO 2 under homogeneous catalyst

In 2003, Ruben Martin and his colleagues showed their experiments on catalyzed direct carboxylation of benzyl halides with CO2 This research illustrated the development of a user-friendly and operationally simple catalytic protocol without sensitive and expensive metal complexes [11]

Ni-Scheme 1.7: Ni-Catalyzed Carboxylation of alkyl halides with CO 2 [11]

However, this method still had some disadvantages:

+ No catalyst separation

+ Using PCp3-a phosphor compound is not safe and should be limited, because

of the noxious phosphor

Ni- MOF used as heterogeneous catalyst in this reaction was not previously reported in the literature.Therefore, in more details,the utilization of a highly porous metal-organic framework Ni2(BDC)2(DABCO) as an efficient heterogeneous catalyst for carboylation with CO2 would be investigated The proposed reaction is shown below

Scheme 1.8 Ni-MOF carboxylation of benzyl halides

1.3 Metal- Organic Frameworks

1.3.1 Introduction

Metal – Organic frameworks (MOF) are hybrid crystalline materials featuring metal-based nodes connected by organic linkers The material MOFs prossess several specific properties such as high porosity, large surface area, high chemical, and physical durability They are useful in gas storage, adsorption-based gas/vapor separation, shape/size-selective catalysis, drug storage and delivery, and as templates for low dimensional material preparation

Being published by Prof O Yaghi in the late 1990s and were recognized by

chemists from all over the world, 20 years later nearly 13000 of MOFs have

been successfully synthesized [12]

Figure 1.3: Number of publications on MOFs over the past decade

1.3.2 Structure

The possibilities in combination of two components, metal ion or cluster and

organic linker, provide MOFs with unique chemical versatility along with

tunable pore size and adjustable surface properties

Figure 1.4: General structure of MOFs [13]

Figure 1.5: Some different MOFs’ structures [14]

Because of the multidimensional structures of MOFs, the linkers need to have two or more similar functional groups per linker A variety of linkers could be listed as polycarboxylate, phosphonate, sulfonate, imidazolate, amine, pyridyl, phenolate [14] By modifying the linkers, scientist can adjust the pore size and the surface area of MOFs to the expected value

Figure 1.6: Aromatic dicarboxylates varying in length used as linkers [13]

1.3.3 Synthetic methods of MOFs

The salt (nitrate, perchlorate, halide or hydroxide) used as a metal source and mixed with organic linker together with solvent to form a liquid mixture before going through the crystallized stage As have been said above, physical properties of a MOFs could be changed by which functionalized organic linker

is used [13] Solvent could be pure, unique solvent or mixture but it must dissolve all metal source, organic linker and auxiliary compounds The structure

of product was affected by the polarity of solvent (or mixture) [15]

There was a wide range of synthetic methods of MOFs from the traditional one like solvent evaporation to the most modern one including microwave reaction, and ultrasonic method, or solvothermal method [16]

However, the most common method was the hydro(solvo)thermal method, which was originally used for the synthesis of zeolites, but has been adapted to the synthesis of MOFs [17] Hydrothermal synthesis uses water as solvent while solvothermal refers to organic solvents Solvents were chosen according to the solubility of organic ligans and metal salts, in some cases two or more than two organic solvents were mixed together Reaction mixture was contained in capped vials, and normally heated at temperature ranging from 80oC to 220oC during several hours or several days Thanks to its simplicity and stability, hydro (solvo) thermal method has become the most popular to synthesize many MOFs [18-20]

1.3.4 Properties

1.3.4.1 High porosity:

The porosity of MOFs is one of the distinguishable factors as compared to other porous materials In term of physical chemistry, the high porosity system of a solid crystal expresses the adsorption capacity According to Furukawa’s research, MOF-210 exhibits the highest BET (Brunauer-Emmett-Teller) of

6240 m2.g-1, Langmuir surface area of 10400 m2.g-1) and pore volume of 3.6

cm3.g-1 [21] Moreover, the largest reported pore aperture is 32 Å and largest reported internal pore diameter is 47 Å, which are found in MOF-74 by Hexiang Deng and his partners [22] These properties enable these MOFs as good candidates for gas storage and gas separation applications [23]

1.3.4.2 Open metal sites:

Several MOFs have open metal sites (coordinative unsaturated) that are built into the pore “walls” in a repeating, regular tendency These metal sites show their potential in catalyst, the partial positive charges on the material also have the potential to enhance general adsorption properties For example, Walton

et al examined adsorption properties of MOFs with open metal sites BTC ) in the separation of carbon monoxide from mixture containing methane, nitrogen, and hydrogen These open metal sites enhance Van Der Waals interactions between Cu-BTC and carbon monoxide, therefore carbon monoxide is separated from gas mixture [24, 25]

(Cu-1.3.4.3 Other properities:

A noticeable property of MOFs is low thermal stability, which is considered as

a weakness of MOFs Several reports pointed out that the decomposition temperature for many of these structures are around 300oC [26] This limits the applications of MOFs However, MOFs using imidazole linkers called ZIF (zeolitic imidazolate framework) possesses a good thermal stability (over

600oC) [27] This promises a great chance to improve the thermal stability of MOFs by modifying the linkers or the dimensional structures

Moreover, a majority of MOFs cannot handle with wide range of pH Provided that the linkers are robust, this chemical stability depends on the cation coordination [28] Another MOFs issue relates to their moisture sensitivity [29-32] However, this disadvantage can be improved by using appropriate functional groups in the MOFs structures [33]

1.3.5 Application of MOFs

Due to their specific properties, MOFs have been applied in many fields such as gas storage, gas seperation, adsorbent, drug delivery, heterogeneous catalysis, sensors [13] Among of them gas storage, gas seperation and heterogeneous catalysis may be the applications gaining most of scientist’s attention in recent years

Figure 1.7: Possible applications of MOFs in various areas [13]

o Gas storage

Carbon dioxide capture has been one of the hottest topics of MOFs research in recent years because CO2 is abundant, inexpensive, nonflammable and attractive as an environmentally friendly chemical reagent [14, 34]

Figure 1.8: The ability of MOF adsorption as compared to the traditional adsorption

[35]

Besides CO2 adsorption, CH4 storage also attracts the interest of scientists Methane is a good candidate for an alternative fuel because it is inexpensive with clean-burning characteristics Moreover, the huge reserves of natural gas (>95% CH4), with some ethane, nitrogen, higher hydrocarbons, and carbon dioxide) around the world are comparable to the energy content of the world’s petroleum reserves Therefore, in order to utilize this CH4, MOFs are considered as the affordable means of transportation and storage [36]

Figure 1.9 : Gravimetric uptake curves of CH4, CO2, H2 and N2 on SIFSIX-3-Zn MOF

[37]

o Gas separation

Gas separation is the most common application of adsorbent materials, where it

is important to consider not only the adsorption equilibrium but also the adsorption kinetics [38] The open metal sites of MOFs obtain much potential

in gas separation

o Catalysis

Scientists all over the world have been attracted by the potential of MOFs in catalysis Not surprisingly, there has been a significantly increased number of

paper researches on catalytic activation of MOFs [39, 40] They can become catalyst for a multitute of reactions

The catalytic activity of MOFs can be attributed to the metal center and the functionality on organic struts, therefore, they become potential materials for reaction catalyst [41] Besides, because of crystalline materials, the MOF catalyst could be easily isolated from the reaction mixture by simple filtration, and could be reused without significant degradation in activity [42]

1.4 Potential of Nickel- MOFs in Catalysis

Nickel is a potential metal that can replace the main role of palladium in a variety of organic transformations [43] This is really an economic solution when facing the large expenditure of palladium Initially, researches on the catalytic activity of this metal in organic reactions are mostly conducted in homogeneous catalyst reactions

Recently, when the green chemistry poses more strict requirements in limiting the amount of hazardous waste discharged into the environment together with removing the metal traces from products, heterogeneous catalyst meets theses needs One of the attractive research nowadays is how can attach the nano-metal into metal-organic frameworks in order to provide the highest reaction yield

In 2010, Kim and colleagues had used the Nickel nanoparticles which were attached to the MOF-1 to catalyze the hydrogenation reaction of nitrobenzene and styrene [44]

Scheme 1.9: The hydrogenation with catalytic nickel nanoparticles embedded in MOF-1

[44]

Similarly, Chou and co-workers pointed out that nickel nanoparticles supported

on MOF-5 could be a good catalyst for the hydrogenation reaction of crotonaldehyde Ni in MOF-5 displayed much higher catalytic activity in comparison with that of the industrial catalyst Ni/SiO2 Furthermore, the catalyst could be reused for several times with the preservation of MOF-5 structure [45]

Scheme 1.10: The hydrogenation with Nickel nanoparticles supported on MOF-5 [45]

Moreover, the scientists developed the use of nickel as metal centers in MOFs, creating a series of heterogeneous catalytic potential for coupling reactions Some of outstanding MOF catalysts at that time were Ni(HBTC)(BPY),

Ni3(BTC)2, Ni2(BDC)2(DABCO) In 2013, Nam T.S Phan and colleagues examined the catalytic activity of Ni(HBTC)(BPY) to the coupling reaction between phenylboronic acid and benzaldehyde, the reaction was carried out at

100oC during 6- hour performance in order to gain 80% of yield [46]

Scheme 1.11:The arylation of aldehydes with arylboronic acids using Ni(HBTC)(BPY)

catalyst [46]

In 2014, Thanh Truong and co-workers’ research had showed the application of the Ni-MOF Ni2(BDC)2(DABCO) as an efficient and selective heterogeneous catalyst for the oxidative cross-coupling reaction between phenylboronic acid with phenylacetylene [50]

Scheme 1.12: The cross-coupling reaction of phenylacetylene and phenylboronic acids

using the Ni 2 (BDC) 2 (DABCO) as catalyst [50]

In the same year, the C–C cross coupling reaction viadirect C–H functionalization using a nickel heterogeneous catalyst namely

Ni2(BDC)2(DABCO) has reported by Nam T S Phan, Chung K Nguyen and Thanh Truong

Scheme 1.13: The direct heterocycle C–H arylation reactions between azoles and

arylboronic acids using Ni 2 (BDC) 2 (DABCO) as a catalyst [51]

Tetsuaki Fujihara, Yuichiro Horimoto, Taiga Mizoe, Fareed Bhasha Sayyed, Yosuke Tani, Jun Terao, Shigeyoshi Sakaki and Yasushi Tsuji had described the reactions proceed under CO2 (1 atm) at room temperature in the presence of

a nickel catalyst, Zn powder as a reducing reagent, and MgBr2 as an indispensable additive Various internal alkynes were converted to the corresponding maleic anhydrides in good to high yields DFT calculations disclosed the indispensable role of MgBr2 in the second CO2 insertion[52]

Scheme 1.14 Nickel-catalyzed double carboxylation of various internal alkynes

To conclude, Ni2(BDC)2(DABCO) had potential in the field of heterogeneous catalysis and should be further exploited In this thesis, Ni2(BDC)2(DABCO) is also used as an efficient and selective heterogeneous catalyst for the direct carboxylation of akyl halides with CO2, which have not been conducted in previous literature

1.5 Nickel-catalyzed carboxylation of Aromatic Compounds with Carbon Dioxide

Carbon dioxide (CO2) is the most abundant renewable carbon source in nature, inexpensive, nonflammable and attractive as an environmental-friendly chemical reagent Chemical fixation CO2 is therefore one of the most important subjects in organic synthesis and much effort has been devoted to this particular subject A large number of inorganic, organic, and metal catalysts have been developed for various chemical conversions of CO2

The synthesis of cyclic carbonates or polycarbonates from CO2 and epoxides, carboxylation reactions with CO2, reduction of CO2, and other fascinating reactions have been developed and studied extensively and intensively [53] (Figure 1.10)

Figure 1.10 Examples of chemical fixation of CO2 [52]

Thierry León, A.C, and Ruben Martin, in 2013, described carboxylation reaction proceeds under mild conditions (atmospheric CO2 pressure) at room temperature Unlike other routes for similar means, their method does not require well-defined and sensitive organometallic reagents and thus is a user-friendly and operationally simple protocol for assembling phenylacetic acids [54]

Scheme 1.15 Synthesis of phenylacetic acids

Scheme 1.16 Carboxylation of secondary and tertiary alkyl halides

Yu Liu, Josep Cornella and Ruben Martin had described the method using a Ni-catalyzed carboxylation of inactivated primary alkyl bromides and sulfonates with CO2 at atmospheric pressure The method was characterized by its mild conditions and remarkably wide scope without the need for air- or moisture-sensitive reagents, which make it a user-friendly and operationally simple protocol en route to carboxylic acids Ni-MOF in catalysis [55]

defined sensitive metal species required

Well-Scheme 1.17 Mechanistic experiments

Then, in November, 2013, Yu Liu, Josep Cornella and Ruben Martin continued

describing a method by using a Ni-catalyzed carboxylation of C(sp2)− and C(sp3)−O Bonds with CO2 [10]

Scheme 1.18 Optimization of the Reaction Conditions

Tetsuaki Fujihara, Keisuke Nogi, Tinghua Xu, Jun Terao and Yasushi Tsuji had described the reactions proceeded under a CO2 pressure of 1 atm at room temperature in the presence of nickel catalysts and Mn powder as a reducing agent Various aryl chlorides were converted to the corresponding carboxylic acid in good to high yields Furthermore, vinyl chlorides are successfully carboxylated with CO2 [56]

Scheme 1.19 Nickel-catalyzed carboxylation of vinyl chlorides

Ni2(BDC)2(DABCO) was published in 2008 used to survey N2 adsorption capacity and CO2 gas, but did not cause a lot of attention [31] Another name of

Ni2(BDC)2(DABCO) is USO-2-Ni, was synthesized from salt Ni(II) and 2 types

of ligand :1,4-benzenedicarboxylic acid and 1,4-diazabicyclo [2.2.2] octane In

2012, author Yves Chabal J had shown the advantage of USO-2-Ni as wet strength and dense metal density within the structure [32]

Moreover, in 2014 Tan and Liang exposed a series of isostructural

M2(BDC)2(DABCO) pillared-paddlewheel MOFs to water vapor and found that the Ni(II) congener displays the highest stability toward linker displacement by water (M = Co(II), Ni(II), Cu(II) or Zn(II) ), which would allow their consideration for application requiring gas sorption, and framework stability in the presence of water, which would render them more suitable for use in industrial setting [33]

Figure 1.11 Ni-Based MetalOrganic Frameworks Containing Paddle-Wheel Type

Inorganic Building Units via High-Throughput Methods [33]

CHAPTER 2: EXPERIMENTALS

2.1.1 Materials and instrumentation

All chemicals needed for synthesizing Ni2(BDC)2(DABCO) were purchased and used as received without further purification Those chemicals are listed in table below

Table 2.1: List of chemicals needed for synthesizing Ni 2 (BDC) 2 (DABCO)

A number of physical methods are used in the survey and analysis :

 X-ray powder diffraction (XRPD) patterns were recorded using a Cu-Kα radiation source on a D8 Advance Bruker powder diffractometer

 Fourier transforminfrar ed (FT-IR) spectra were obtained on a Nicolet 6700 instrument, with samples being dispersed on potassium bromide pallets

 Nitrogen physisorption measurements were conducted using a Micromeritics 2020 volumetric adsorption analyzer system Samples were pretreated by heating under vacuum at 150 oC for 3 h

 A Netzsch Thermoanalyzer STA 409 was used for thermogravimetric analysis (TGA) with a heating rate of 10oC/min under a nitrogen atmosphere

 The ICP (Inductively coupled plasma) was used to identify the amount

Figure 2.1: Structure simulation of Ni2(BDC)2(DABCO) [57]

In a typical preparation [57], a solid mixture of H2BDC (H2BDC = benzenedicarboxylic acid; 0.332 g, 2 mmol), DABCO (DABCO = 1,4-diazabicyclo(2.2.2)octane; 0.168 g, 1.5 mmol), and Ni(NO3)2.6H2O (0.58 g, 2

1,4-mmol) was dissolved in DMF (DMF = N,N’-dimethylformamide; 15 ml) The

resulting solution was distributed to two 20 ml vials The vials were then heated

at 100 oC in an isothermal oven for 48 h After cooling the vials to room