Reactions of Water-Soluble Iridium Complexes with Alkynes and Alcohols : Water-Souluble Iridacycles and η³-Allyl-Alkenyls

김경환 서강대학교 대학원 2002 국내석사

수용성 비스-히드리도 화합물 [Cp*Ir(H)_2PAr_3] (1)은 메탄올에서 [Cp*Ir(Cl)_2PAr_3]과 NaOMe의 반응으로부터 높은 수율로 생성되었다. 화합물 1은 D_2O와의 반응으로 d_2동위 원소체인 [Cp*Ir(D)_2PAr_3] (1-d_2)을 형성한다. 화합물 1은 물에서 HBF_4와 반응하여 비스-아쿠아 화합물 [Cp*Ir(OH_2)_2PAr_3](BF_4)_2 (2)를 생성한다. 화합물 1은 PHCOOH와의 반응으로 [Cp*Ir(OCOPh)(H)PAr_3] (3)와 [Cp*Ir(OCOPh)_2PAr_3] (4)를 형성한다. 화합물 1은 H_2O/Benzene용매에서 알킨 (H-CC-CH_2Cl)과 반응하여 알케닐-카르보닐 화합물 [Cp*Ir(CO)(-CH=CH_2)PAr_3]Cl (5)을 형성한다. 수용성 니트릴 화합물 [Cp*Ir(NCR)(Cl)PAr_3]OTf (6, R = CH_3 (a), CH_2CH (b))은 메탄올에서 1당량 AgOTf와 RCN의 반응으로부터 얻어졌다. 화합물 6은 PAr_3 P(m(-C_6H_4SO_3Na)3) 존재하에 1당량 AgOTf와 반응하여 화합물 [Cp*Ir(NCMe)(PAr_3)_2](OTf)_2 (7) 을 형성한다. 화합물 6은 알킨 HCCPh과 반응하여 [Cp*Ir(CO)(Cl)PAr_3]OTf (8)과 유기물 (C_6H_5CH_2OH, C_6H_5CH_3)을 형성 한다. 카르보닐 화합물 [Cp*Ir(CO)(Cl)PAr_3]Cl는 NaOR 과 반응하여 알콕시기의 카르보닐 카본에 친핵성 공격에 의한 화합물 알콕시카르보닐 [Cp*Ir(-C=OOR)(Cl)PAr_3] (9, R = Me(a), Et(b))을 형성한다. 수용성 Iiridacycle 화합물 [Cp*Ir(=C(OR)CHCHCH_2)PAr_3]OTf (10, R = CH_3(a), CH_3CH_2(b), CH_3CH_2CH_2(c))은 알코올 (ROH)과 알킨 (HCCH)과의 반응을 통해 각각 합성되었다. 이 반응은 배위된 아세틸렌에 알코올의 공격이 개시 단계로 보인다. Cd_3OD에서의 이 반응은 동위 원소체인 [Cp*Ir(=C(OCd_3)CHCHCH_2)PAr_3]OTf (10a-d_3)을 형성한다. 비수용성 화합물 [Cp*Ir(=C(OR)CHCHCH_2)PPh_3]OTf (10-1) 또한 같은 방법으로 [Cp*Ir(NCMe)_2PPh](OTf)_2)와의 반응을 통해 합성하였다. 화합물 10a는 NaBH_4와 반응하여 미지의 단일화합물을 형성한다. 비수용성 화합물 [Cp*Ir(NCMe)(3-CH_2CHCHPh)]OTf는 PAr_3 존재하에 알킨 HCCH와의 반응을 통해 수용성 3-알릴-알케닐 화합물 [Cp*Ir(3-CH_2CHCHPh)(-CH=CH-+PAr_3)]OTf (11)을 높은 수율로 얻어진다. 결과적으로, 알킨이 [Cp*Ir(NCMe)_2PAr_3](OTf)_2의Ir-PAr_3결합안으로의 삽입된 것이다. Water-soluble bis-hydrido complex [Cp*Ir(H)_2PAr_3] (1) has been prepared in high yield from the reaction of [Cp*Ir(Cl)_2PAr_3] with NaOMe in MeOH. Complex 1 reacts with D_2O to give the d_2 isotopomer [Cp*Ir(D)_2PAr_3] (1-d_2). Reaction of 1 with HBF_4 in H_2O produce the bis-aqua complex [Cp*Ir(OH_2)_2PAr_3](BF_4)_2 (2). Reactions of 1 with PhCOOH give to complexes [Cp*Ir(OCOC_6H_5)(H)PAr_3] (3) and [Cp*Ir(OCOC_6H_5)_2PAr_3] (4). Reaction of 1 with alkyne (HCCHCH_2Cl) in H_2O/Benzene produce the alkenyl-carbonyl complex [Cp*Ir(CO)(-CH=CH_2)PAr_3]Cl (5). Water-soluble nitrile complex [Cp*Ir(NCR)(Cl)PAr_3]OTf (6, R = CH_3 (a), CH_2CH (b)) have been prepared from the reaction of [Cp*Ir(Cl)_2PAr_3] with 1 equiv AgOTf and RCN in MeOH. Complex 6 reacts with 1equiv AgOTf in the presence of PAr_3 (P(m-C_6H_4SO_3Na3)) to give [Cp*Ir(NCR)(PAr_3)_2](OTf)_2 (8) (R = CH_3 (a), CH_2CH (b)). Complex 6 reacts with alkyne HCCPh to give [Cp*Ir(CO)(Cl)PAr_3]OTf (7) and organics (C_6H_5CH_2OH, C_6H_5CH_3). Reactions of the Carbonyl complex [Cp*Ir(CO)(Cl)PAr_3]Cl with NaOR produce the alkoxycarbonyl complexes [Cp*Ir(COOR)(Cl)PAr_3] (9, R = OMe (a), OEt (b)) by nucleophilic attack of alkoxy group on the carbonyl carbon. Water-soluble iridacycle complexes [Cp*Ir(=C(OR)CHCHCH_2)PAr_3)]OTf (10, R = CH_3 (a), CH_3CH_2 (b), CH_3CH_2CH_2 (c)) have been prepared from the reaction of [Cp*Ir(NCMe)_2PAr_3](OTf)_2 with alkyne (HCCH) in alcohol ROH, respectively. Attack of ROH on the coordinated acetylene on the acetonitrile seems to be the initial step for the formation of 10, respectively. This reaction in Cd_3OD with HCCH give isotopomer [Cp*Ir(=C(OCd_3)CHCHCH_2)PAr_3]OTf (10a-d_3). Water-insoluble iridacycle complexes [Cp*Ir(=C(OR)CHCHCH_2)PPH_3)]OTf (10-1, R = CH_3 (a), CH_3CH_2 (b), CH_3CH_2CH_2 (c)) have been also prepared from the reaction of [Cp*Ir(NCMe)_2PPh_3](OTf)_2 with alkyne (HCCH) as the same method. Water-insoluble complex [Cp*Ir(3-CH_2CHCHPh)(NCMe)]OTf reacts with alkynes (HCCH) in the presence of PAr_3 to give water-soluble 3-allyl-alkenyl complex [Cp*Ir(3-CH_2CHCHPh)(-CH=CH+PAr_3)]OTf (11) in high yields. Effectively, alkynes insert into the Ir-P bonds of [Cp*Ir(3-CH_2CHCHPh)PAr_3)]OTf.

Model Complexes for Extradiol and Intradiol dioxygenase : Properites and Reactivity of [Fe^(II)(DIPBA)(DBCH)] and [Fe^(III)(BIABP)(DBC)]

조준용 高麗大學校 大學院 2003 국내석사

HDIABA, HDIPBA, and HBIABP have been synthesized for model complexes that mimic five coordinate iron centers found in the active sites of extradiol and intradiol dioxygenase-substrate complexes, where HDIABA is 2-[(1-methyl-4,5-diphenylimidazol-2-ylmethyl)-amino]-benzoic acid, HDIPBA is 2-[(1-methyl-4,5-diphenylimidazol-2-ylmethyl)-amino]-6-phenyl-benzoic acid, and HBIABP is 3-{[benzyl-(1-methylbenzimidazol-2-ylmethyl)-amino] -methyl}-biphenyl-2-ol. Model complexes, [Fe^(Ⅱ)(L)(CatH)] and [Fe^(Ⅲ)(L)(Cat)], have been synthesized under inert condition and characterized by NMR, EPR, electronic spectral, and electrochemical methods. [Fe^(Ⅱ)(DIABA)(DBCH)] (1a) and [Fe^(Ⅱ)(DIABA)(BphCH)] (2a) are the new structural model complexes with the carboxylate moiety for extradiol dioxygenase-substrate complex, where DBCH is 3,5-di-tert-butyl catecholate monoanion, and BphCH is biphenyl catecholate monoanion. The electronic spectra of 1a and 2a in CH_(3)CN show intense bands at ∼500nm in the visible region that probably originated from the Fe^(Ⅱ)-to-catecholate charge transfer transition. ^(1)H NMR spectrum of 1a and 2a do not show any peaks in the paramagnetic region. Moreover, 1a and 2a do not show any EPR signal due to the antiferromagnetic coupling between diiron(Ⅱ,Ⅱ) centers. When 1a and 2a are exposed to dioxygen, they convert to blue species within a minute and become yellow species eventually. The blue species exhibit an absorption band at ∼624nm in CH_(3)CN that can be assigned to catecholate-to-Fe^(Ⅲ) charge transfer transition. This band is same to that of [Fe^(Ⅲ)(DIABA)(DBC)] (1b) or [Fe^(Ⅲ)(DIABA)(BphC)] (2b). Interestingly, ^(1)H NMR spectrum of 1b and 2b also do not show any peaks in the paramagnetic region. Moreover, 1b and 2b do not show any EPR signal due to the antiferromagnetic coupling between diiron(Ⅲ,Ⅲ) centers. Other physical data also show that these complexes form diiron(Ⅲ,Ⅲ) complexes. When adding the strong ligand CN^(-) to 1b and 2b solution, they show absorption bands at 530 and 945nm that are characteristic features of monomeric six-coordinate Fe^(Ⅲ)-catecholate complexes. These results suggest that 1b and 2b might be diiron(Ⅲ,Ⅲ) complexes with (μ-benzoate)bridge due to the lack of steric hindrance of benzoate moiety. HDIPBA is a new designed ligand having substituted benzoate to prevent from the dimerization via (μ-benzoate)bridge between iron(Ⅲ) complexes. However, we had trouble with stablizing [Fe^(Ⅱ)(DIPBA)(DBCH)] complex, probably due to the large steric effect of the HDIPBA ligand. Thus, we can suggest that the best model complex for extradiol dioxygenase-substrate complex need smaller amine moiety with phenyl benzoate, and also needs electronic tunning of the metal center. [Fe^(Ⅲ)(BIABP)(DBC)] is a model complex with terminal phenol moiety for intradiol dioxygenase-substrate complex. (3) is crystallized in monoclinic space group P2_(1/c) with a=12.324(14) A˚, b=18.474(2) A˚, c=18.295(2) A˚, β=98.539(2)°, and Z=4. X-ray crystallographic studies show that 3 is formulated as [Fe^(Ⅲ)(BIABP)(DBC)]_(2) with an inversion center. The structure of 3 can be considered as bis(μ-phenoxo)diiron(Ⅲ,Ⅲ) complex in the solid state having Fe(1)-O(3)=2.018 A˚ slightly shorter than Fe(1)-O(3_3)=2.106 A˚. In the monomeric Fe^(Ⅲ) form, iron(Ⅲ) center has a distorted square pyramidal five-coordinate geometry with N_(2)O_(3) donor set. However, other physical data show that 3 is in the equilibrium between dimeric and monomeric form in solution. ^(1)H NMR spectrum of 3 in acetone-d_(6) shows a typical pattern of high-spin Fe^(Ⅲ)-catecholate complex. 3 exhibits two intense absorption bands at 504,737nm that can be assigned to catecholate-to-Fe^(Ⅲ) charge transfer transitions. The cyclic voltammogram of 3 in CH_(3)CN shows a quasi-reversible half redox potential at +282 mV versus SCE due to DBSQ/DBC couple. The EPR spectrum of 3 in acetone at 4 K exhibits a signal at g=4.3, indicating a high spin Fe^(Ⅲ)(S=5/2) with rhombic symmetry. After the complete oxygenation, 3 is changed to yellow color. Furthermore, it does not show any EPR signals due to the antiferromagnetic coupling between diiron(Ⅲ,Ⅲ) center. When 3 is exposed to dioxygen in CH_(2)Cl_(2), it generates almost same amounts of intradiol cleaved products (39%), extradiol cleaved products (41%), and byproduct 5(10%). Therefore, these results suggest that [Fe^(Ⅲ)(BIABP)(DBC)] complex undergoes both oxygen activation and substrate activation mechanism.

(The) Morphological Consequences of Apartment Complex Building in Seoul

황세원 서울대학교 대학원 2018 국내박사

apartment complex development, morphological characteristics of apartment complex, agglomeration patterns of apartment complexes, neighborhood impacts of apartment complexes, urban form of Seoul, apartment complex urbanism

Experimental Evaluation of Kinetics of Metal-EDTA Complex Formation and Metal-Metal Exchange between Metal-EDTA Complexes

Muhammad Shahzad Khurram 명지대학교 국제대학원 2009 국내석사

EDTA (ethylenediaminetetraacceticacid) is a chelating agent and frequently found in industrial and domestic wastewater. It has an ability to form strong water soluble complexes with a variety of metal cations, is considered to be nonbiodegradable in traditional wastewater treatment processes, and thus interferes with the removal of metals from wastewater. Some metal-EDTA complexes have been known to be amenable to metal-removal processes including biodegradation. And those metal-EDTA complexes that are difficult to be removed could be converted to a metal-EDTA complex that is amenable to its removal. However, it has been reported that metal exchange between some metal-EDTA complexes is not instantaneous. Therefore, metal-exchange kinetics is an important piece of information that will affect the development, design, and operation of metal-removal processes. In this study, the metal-exchange kinetics was experimentally investigated. This study was carried out in three phases. In the first phase, selected metals were reacted with EDTA to understand how fast metal-EDTA complexes are formed. EDTA complexes with the metals, Ca, Co, Cu, Fe (III), Mg, Mn, Ni, Al and Zn, were found to be formed almost instantaneously. In the second phase, the exchange kinetics between a free metal ion and a metal in its metal-EDTA complex for selected metals and metal-EDTA complexes. For each experiment, a pair of metals, whose EDTA complexes have widely different stability constants, were selected and used. The exchange between a free metal and a metal in its metal-EDTA complexes was generally fast (<30 min) when it occurred and seemed to be affected by pH. In general, a metal in its metal-EDTA complex could be replaced by a free metal, which forms a much more stable complex with EDTA than the former complex. In addition, the competition between a selected pair of metals for forming metal-EDTA complexes was studied. The higher solubility constant metal-EDTA complex dominated in concentration when two free metals were reacted with free EDAT, but at pH 10.2 lower stability constant metals shared considerable amount of EDTA. In the third phase the exchange of metals between two metal-EDTA complexes was investigated and found that no exchange of metals between the complexes was observed. Equilibrium constants for each reaction of phases one and two were calculated and compared with published values. It appeared that all reactions in this study reached equilibrium in <30 min. The results of this study would be useful to design physical/chemical/biological processes for removing metal-EDTA complexes.

참당귀로부터 유래된 Decursin complexes의 Nano-emulsion을 통한 상처치료 효과 기능성 개선

한지수 명지대학교 대학원 2017 국내석사

최근 BT 분야의 천연물 이용은 생리활성 물질인 3차 기능성분물질이 건강관리, 다이어트나 미용 혹은 각종 질병예방효과를 기대하여 많이 이용되고 있다. 이와 같은 천연물들은 오랜 기간 생약(生藥)을 비롯한 기능성식품과 기능성화장품 및 각종 민약 (民約) 분야에 많이 활용 되어 왔으며 대체의학(complementary and alternative medicine)에 대한 대중적 관심과 국가 차원의 연구개발정책을 수립하여 지원이 확대되면서 천연물산업은 기능성식품과 기능성화장품 분야에서 첨단 BT기술의 발전과 함께 크게 부상하고 있다. 우리나라와 중국의 동북부 지역의 고랭지역에서 자생하는 참당귀는 미나리과 속 다년생 초본으로 다양한 약리적 효과가 있는 것이 알려져 있어 생약재로 널리 사용되어 왔다. 참당귀의 뿌리, 줄기에는 쿠마린 계열의 다양한 물질이 존재한다는 것이 알려져 있고 대표적인 물질로는 dihydropyranocoumarin 계열의 decursin과 decursinol angelate 가 다량 함유되어 있다는 것이 1967년에 처음으로 밝혀졌다. 참당귀의 다양한 생리활성 작용이 밝혀져 있으나, 혈액 순환 개선을 통한 상처 치료 효과에 대한 명확한 기전은 밝혀지지 않았다. 본 연구에서는 참당귀의 기능성 중 혈액 순환 개선을 통한 상처 치료 효과를 세포수준에서 검증하고 관련 유전자의 발현 양상을 조사함으로써 그 기능을 과학적으로 입증하고자 한다. 또한, decursin 및 decursinol angelate는 hydrophobic compound로서 수용성 물질에 대한 용해도가 상대적으로 낮으며 생체 이용률의 문제를 갖는다. 따라서 nano-emulsion제조 기술을 통해 decursin complexes nano-emulsion을 제조하고 nano-emulsion의 의해 개선된 상처 치료 효과를 통하여 새로운 기능성 소재로서의 가능성을 제시하고자 한다. 먼저, 진부GAP영농조합에서 재배된 참당귀를 수확하여 분쇄, 건조한 것을 주정 알코올을 사용하여 추출하고, MPLC를 사용하여 decursin complexes를 분리하였다. 이렇게 분리된 decursin complexes를 HaCaT (Human Keratinocyte)에 농도별로 처리하여 wound healing 효과를 조사하였고, 0.5 μg/ml의 농도에서 효과적으로 wound healing 효과가 있음을 규명하였다. 그리고 생체 이용률을 증가시키기 위해 decursin complexes nano-emulsion을 제조하고 이 nano-emulsion에 의해 개선된 wound healing 효과를 확인하였다. Decursin complexes nano-emulsion의 농도 0.08 μg/ml에서 가장 효과적인 wound healing 효과를 확인하였으며, decursin complexes의 nano-emulsion의 농도 0.08 μg/ml에서의 wound healing 효과가 nano-emulsion화 하지 않은 동일 농도의 decursin complexes보다 더 효과적인 wound healing 효과를 입증하면서, nano-emulsion화된 decursin complexes가 더 효율적으로 세포내로 흡수되어 wound healing 효과가 개선될 수 있는 가능성을 보여주었다. 이는 산업적으로도 저 농도에서도 뛰어난 생리활성 기능을 구현할 수 있는 제품 개발이 가능하다는 것을 의미하며, 최종 생산단가를 낮추어 경제적으로도 중요한 기술이라 예상된다. 그리고 decursin complexes에 의한 wound healing 효과와 관련된 signaling pathway를 탐색하기 위해서 immunoblotting과 EGFR biosensor 세포주를 이용하였다. Immunoblotting결과, EGFR 유래 signal pathway와는 관련이 없는 것으로 확인되었으며 EGFR biosensor를 이용한 실험에서도 동일한 결과를 확인하였다. 하지만 ERK 단백질의 phosphorylation이 발생하였기 때문에 EGFR유래가 아닌 다른 receptor유래 signal pathway에 의해 wound healing 효과가 나타나는 것으로 예상되었으며 Human wound healing qRT-PCR assay를 이용하여 decursin 및 decursinol angelate 처리에 의한 HaCaT cell 내의 유전자 발현양상을 탐색하였다. decursin을 처리한 HaCaT에서는 ECM remodeling enzyme 중 CTSG 및 F13A1 유전자와 cell adhesion molecules을 발현하는 ITGB2 유전자가 control에 비해 10배 이상 up-regulation되었다. Decursinol angelate 처리군에서는 ECM structural constituents를 발현하는 COL1A1, ECM remodeling enzyme을 발현하는 F13A1, growth factors를 발현하는 FGF10 및 HGF, inflammatory cytokine 유전자를 발현하는 IL10 유전자가 특이적으로 up-regulation이 되었다. 이는 decursin 과 decursinol angelate가 구조적으로 매우 유사하지만 HaCaT 세포주내에서 작용하는 단백질과 기능적으로 다르며 up-regulation된 유전자 수에서도 차이가 나는 것으로 예상할 수 있다. 따라서 참당귀 추출물로부터 분리한 decursin complexes는 wound healing 효과를 지니고 있으며, 이를 nano-emulsion화 했을 때 개선된 효과를 나타냈고, 과학적으로 decursin과 decursinol angelate가 작용하는 단백질이 서로 다르다는 것을 입증하면서 천연물 산업의 원료로서 활용 가능성이 있음을 확인하였다. Recently, physiologically active substances from natural products have been widely used in the BT field for health care, diet, beauty, and various disease prevention effects. These natural products have been used for a long time in the field of functional foods, functional cosmetics and herbal medicines. As public interest in complementary and alternative medicine and support for national R & D have expanded, the natural products industry has emerged with the development of advanced BT technology in functional foods and functional cosmetics. Angelica gigas Nakai which grows in the Korea and northeastern region of China is known to have various pharmacological effects and is widely used as an herbal medicine. It is known that there are various coumarin-based compounds in the roots and stem of Angelica gigas Nakai. It was first discovered in 1967 that a representative compound is a dihydropyranocoumarin-type decursin and decursinol angelate. Various physiological activities of Angelica gigas have been revealed. However, a clear mechanism for wound healing by improvement of blood circulation was not revealed. In this study, we tried to verify the function of wound healing effect through improvement of blood circulation among the functionalities of Angelica gigas Nakai on the cellular level and to prove its function by investigating the expression patterns of related genes. In addition, decursin and decursinol angelate are hydrophobic compounds that have relatively low solubility in water soluble materials and bioavailability problems. Therefore, we have manufactured decursin complexes nano-emulsion through nano-emulsion manufacturing technology, and suggest possibility of new functional material by verifying the improved wound healing effect by nano-emulsion. Angelica gigas Nakai was harvested in Jinbu GAP and ground, dried. It was extracted with ethanol, and decursin complexes were isolated by using MPLC. Separated decursin complexes were treated with HaCaT (Human Keratinocyte) at different concentrations to investigate the wound healing effect, and it was found that the most effective concentration for wound healing effect is 0.5 μg/ml. In order to increase the bioavailability, decursin complexes nano-emulsion was prepared and the improved wound healing effect by this nano-emulsion was confirmed. The most effective concentration of decursin complexes nano-emulsion for wound healing effect was 0.08 μg/ml. It was confirmed that the wound healing effect at 0.08 μg/ml of the decursin complexes nano-emulsion is more effective than the decursin complexes at the same concentration without nano-emulsification. It means that nano-emulsified decursin complexes were more efficiently absorbed into the cells and the wound healing effect could be improved. This means that it is possible to develop a product having an excellent physiological activity at a low concentration in the industry, and it is expected to be an economically important technology because it can lower the final production cost. Immunoblotting was performed and EGFR biosensor cell lines were used to detect signaling pathways associated with wound healing effects by decursin complexes. Immunoblotting results showed that the wound healing effect of decursin complexes was not related to the EGFR signaling pathway, and the same results were obtained with the EGFR biosensor cell lines. However, due to the phosphorylation of ERK protein, it was expected that the wound healing effect would be caused by the signal pathway derived from other receptor. So, human wound healing qRT-PCR assay was used to detect gene expression patterns in HaCaT cells by decursin and decursinol angelate treatment. In decursin-treated group, CTSG and F13A1 genes related to ECM remodeling enzyme and ITGB2 gene expressing cell adhesion molecule were over 10 times up-regulated compared to the control. In the decursinol angelate-treated group, COL1A1 gene expressing ECM structural constituents, F13A1 gene expressing ECM remodeling enzyme, FGF10 and HGF genes expressing growth factors and IL10 gene expressing the inflammatory cytokine were specifically up-regulated. There results suggest that although decursin and decursinol angelate are structurally very similar, they function differently in HaCaT cell lines and the number of up-regulated genes are also different. Therefore, the decursin complexes isolated from Angelica gigas Nakai have wound healing effect, which showed an improved effect when nano-emulsified, and scientifically proved that decursin and decursinol angelate function differently from each other. These results mean that it can be used as a raw material in the natural products industry.

Reactivity of Cationic Cp*Ir Complexes with Three Labile Ligands : Alkyne Insertion into Ir-L (L = PPh3, P(m-C6H4SO3Na)3) and Direct Ring Methyl Activation of Pentamethylcyclopentadienyl Ligands

김윤호 서강대학교 대학원 2002 국내석사

A Cl이 한 자리 배위 되어있는 수용성 금속 화합물인 Cp^*IrCl(PAr_3)_2 (2)에 HCCH이 삽입 반응하여 한 자리의 알케닐이 배위된 [Cp*IrCl(CH=CHPAr_3)(PAr_3)](OTf) (3) 이 합성되어지는 반면에 수용성 리간드인 PAr_3 존재 하에서는 두 분자의 HCCH이 삽입 반응하여 알케닐이 두 자리 배위된 [Cp*Ir(CH=CHPAr_3)_2(PAr_3)](OTf)_2 (4)이 합성되어진다. 2와 비교해 비수용성 이리��화합물인 Cp*IrCl(PPh_3)_2 (5)은 과량의 PPh_3 존재 하에서도 한 분자의 HCCH이 삽입 반응하여 한 자리의 알케닐 화합물인 [Cp*IrCl(CH=CHPPh_3)(PPh_3)](OTf)_2 (6)을 준다. 하지만 세 개의 레바일 자리를 갖는 Cp*Ir(NCCh_3)_3 (7) 과 HCCH을 반응시키면 두 자리의 알케닐이 배위 된 비수용성 금속 화합물인 [Cp^*Ir(CH=CHPPh_3)_2(PPh_3)](OTf)_2 (7)이 만들어 진다. 이러한 결과는 이미 알려져 있듯이 수용성 Ir화합물에서의 Cl이 비수용성의 Ir화합물에서의 Cl 보다 좀 더 레바일 하여 생기는 결과이다. B 세자리 레바일 [Cp^*Ir(L)_3](OTf)_2 (L = CH_3N (a), (CH_3)_2CO(b)) (1)은 높은 반응성이 있는 것으로 알려져 있다. 아세토나이트릴 용매 하에서 1과 PPH_3과 반응하여 고리 멜틸기의 활성화된 즉, Cp^*의 고리에 있는 메틸기의 수소가 PPH_3으로 치환된 [(C_5Me_4CH_2PPH_3)Ir(H)(PPH_3)_2](OTf)_2 (2)을 준다. 이 반응에서 먼저 PPH_3이 이리듐에 배위되고 PPH_3이 Cp^*의 메틸기의 탄소를 공격함으로서 수소가 이리듐으로 이동하여 생기는 것으로 보인다. 그러나 이와 같은 반응은 알코올 용매 존재 하에서는 고리 메틸기의 활성화된 금속 화합물을 주지않고 수소가 이리듐에 배위 되어있는 [Cp^*Ir(H)(PPH_3)_2] (OTf)_2 (3)을 준다. 이러한 Ir-H의 H는 알코올의 CH_3로부터 오는 것을 중수소 실험과 물에서의 반응의 결과로부터 확인 할 수 있었다. 2번 화합물의 중간체를 얻기 위하여 반응시간을 짧게(1 h)하고 재결정을 하기 위하여 CHCl3를 넣었더니 뜻밖에도 Cl이 배위 되어진 [(C_5Me_4CH_2PPH_3)Ir(Cl)(PPH_3)_2](OTf)_2 (4) 생성되었다. 이렇게 합성된 4를 가지고 아세틸렌과 반응시켜 알케닐 화합물인 [(C_5Me_4CH_2PPH_3)Ir(CH=CHPAr_3) (PPH_3)_2](OTf)_2 (7)을 얻었고 이와 더블어 4와 MeI를 반 시켜 배위 된 PPH_3이 I로 치환된 [(C_5Me_4CH_2PPH_3)Ir(Cl)(I)(PPH_3)](OTf)_2 (8)을 얻었다. 또한 8에 AgOTf를 반응시켜 두 자리의 레바일 자리를 갖는 [(C_5Me_4CH_2PPH_3)Ir(CH_3CN)_2(PPH_3)](OTf)_3 (9)을 얻었다. 다음으로 이러한 두 자리 레바일한 9번 화합물을 가지고 반응성 실험을 하였다. 그래서 우선 아세토나이트릴 존재 하에서 9에 PPH_3을 넣고 반응시키면 고리 메틸이 두 번째로 활성화된 [(C_5Me_3(CH_2PPH_3)_2)Ir(H)(PPH_3)_2](OTf)_3 (10)을 생성한다. 아세틸렌 존재 하에서 9와 PPH_3와의 반응은 두 자리의 알케닐이 배위된 for [C_5(CH_3)4CH_2PPH_3Ir(CH=CHPPH_3)_2(PPH_3)](OTf)_3 (11) 생성된다. 또한 아민 존재 하에서 CHC-p-tolyl과 반응시키면 두 개의 알카인기가 배위 되어 있는 [(C_5Me_4CH_2PPH_3)Ir(CHC-p-tolyl)_2-(PPH_3)](OTf) (12)이 생성된다. 이러한 실험을 바탕으로 수용성 리간드인 PAr_3을 이용하여 아세토나이트릴과 물 용매하에서 1과 PAr_3을 반응시켜 수용성 고리 메틸 활성화 화합물인 [(C_5Me_4CH_2PAr_3)Ir(H)-(PAr_3)_2](OTf)_2 (13)을 얻었다. 알코올 용매하에서 1과 PAr_3을 반응시키면 수소가 이리듐에 배위된 [(C_5Me_4CH_2PAr_3)Ir(H)(PAr_3)_2] (OTf) (14)이 생성된다. A Reactions of Cp^(*)IrCl(PAr_(3))_(2) (2) with HCCH give [Cp^(*)IrCl(CH=CHPAr_(3))(PAr_(3))](OTf) (3) in water while [Cp^(*)Ir(CH=CHPAr_(3))_(2)(PAr_(3))](OTf)_(2) (4) are obtained from that in the presence of PAr_(3). Water-insoluble analogue of 2, Cp^(*)IrCl(PPh_(3))_(2) (5) react with HC=CH not to give bis(alkenyl)-iridium(Ⅲ) complexes but to give [Cp^(*)IrCl(CH=CHPPh_(3))(PPh_(3))](OTf)_(2) (6) even in the presence of excess PPh_(3) while water-insoluble analogue of 3, [Cp^(*)Ir(CH=CHPPh_(3))_(2)(PPh_(3))](OTf)_(2) (7) are obtained from that of Cp^(*)Ir(NCCH_(3))_(3) (7) with HCCH in the presence of PPh_(3). These results suggest that the Cl of 2 is more labile than that of 5. This lability of Cl of water-soluble iridium complexes is previous reported. B Three-labile [Cp^(*)Ir(L)_(3)](OTf)_(2) (L = CH_(3)N (a), (CH_3)_2CO(b)) (1) are high reactive complexes have been known. Reactions of [Cp^(*)Ir(L)_(3)](OTf)_(2) (L = CH_(3)CN (a), (CH_(3))_(2)CO (b)) (1) with PPH_(3) in CH_(3)CN afforded a ring-methyl activation complex [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(H)(PPH_(3))_(2)](OTf)_(2) (2). It seems that reactions of cationic complexes 1, coordination of the phosphine to the iridium center would occur at first. Phosphine attacked ring-methyl in the cationic Cp^(*) complex could take place to afford a migration of hydrogen to Ir center and formation of 2. But reactions of [Cp^(*)Ir(L)_(3)](OTf)_(2) (L = CH_(3)CN (a), (CH_(3))_(2)CO (b)) (1) with PPH_(3) in alcohol afforded a hydrido complex [Cp^(*)Ir(H)(PPH_(3))_(2)] (OTf)_(2) (3). And surprisingly it seems the hydride moiety of 3 bring from C-H of CH_(3)OH in the deuterium experiment results. In order to get an intermediate for this reaction, I stopped this after a moment (ca. 1 h), recrystallized with CHCl3/ether. It gives an unexpected reaction product which was a chloro-contained iridium complex [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(Cl)(PPH_(3))_(2)] (OTf)_(2) (4). Ring methyl activated complex [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(Cl)(PPH_(3))_(2)] (OTf)_2 (4) reacts with HCCH to give alkenyl-iridum(Ⅲ) complexes [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(CH=CHPPH_(3))(Cl)(PPH_(3))](OTf)_(2) (7). Also 4 is readily displaced by a smaller I- in the reactions of MeI to give complex [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(Cl)(I)(PPH_(3))](OTf)_(2) (8). A reaction of 8 with AgOTf in CH_(3)CN afforded a two labile complex [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(CH_(3)CN)_(2)(PPH_(3))](OTf)_(3) (9). A reaction of two labile ring methyl activated [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(CH_(3)CN)_(2)(PPH_(3))](OTf)_(3) (9) with PPH_(3) in CH_(3)CN afforded a second ring-methyl activated complex [(C_(5)Me_(3)(CH_(2)PPH_(3))_(2))Ir(H)(PPH_3)_(2)](OTf)_(3) (10). A reaction of two labile ring methyl activated (9) with PPH_(3) under HCCH afforded a ring-methyl activated bis(alkenl)-complex [(C_(5)Me_(4)CH_(2)PPH_(3))Ir-(CH=CHPPH_(3))_(2)(PPH_(3))_(2)](OTf)_(2) (11). The bis(alkynyl)-iridum(Ⅲ) complexes [(C_(5)Me_(4)CH_(2)PPH_(3))Ir(CHC-p-tolyl)_(2)(PPH_(3))](OTf) (12) have been prepared from the reaction of ring methyl activated two labile complex [(C_(5)Me_(4)CH_(2)PPH_3)Ir(NCCH_(3))_(2)(PPH_(3))](OTf)_(3) (9) with HCCH (R = p-tolyl) in the presence of NEt3. In order to application of water soluble system, three-labile complexes 1 reacts with PAr_(3) to give water soluble ring methyl activated complex [(C_(5)Me_(4)CH_(2)PAr_(3))Ir(H)-(PAr_(3))_(2)](OTf)_(2) (13) in H_(2)O/CH_(3)CN. three-labile complexes 1 reacts with PAr_(3) in alcohols to give water soluble hydrido complex [(C_(5)Me_(4)CH_(2)PAr_(3))Ir(H)(PAr_(3))_(2)] (OTf) (14) in alcohol.

Empirical study on a logistics platform for optimizing logistics in industrial complexes

김정하 Graduate School, Yonsei University 2024 국내박사

This study investigates the necessity of sharing logistics resources among companies in industrial complexes and examines the government's "Smart Logistics Platform Construction and Operation Project" through systematic strategies to verify its performance and suggest policies for efficient logistics platform construction. Industrial complexes, as regions where manufacturing companies are concentrated, play a crucial role in logistics among resident companies. However, concerns arise due to the increasing number of aging industrial complexes over 20 years old and the continuous decline in operation rates, leading to potential employment crises. To address these issues, the government actively promotes the "Smart Logistics Platform Construction and Operation Project," aiming to transform industrial complexes into low-carbon, high-efficiency, and eco-friendly areas, particularly by digitizing the logistics environment through a logistics platform project. This study also identifies logistical challenges in industrial complexes and systematically establishes a logistics platform business. A preliminary survey was conducted to select target industries for the logistics platform, focusing on the hypothesis that introducing a logistics platform within an industrial complex would create synergies among companies within the same industry or supply chain system. The automotive industry in the Ulsan region was chosen as the target for the introduction of the logistics platform. A survey and analysis were conducted on the necessity and willingness to use four services provided by the logistics platform: “Joint Logistics Center,” “Joint Transportation Service,” “Logistics Resource Sharing Service,” and “Logistics Information Service.” Additionally, an importance-performance analysis (IPA) prioritized the services to be implemented, and a survey addressed logistical operational challenges and problems faced by companies in the complex. In-depth interviews with manufacturing and logistics experts further analyzed the actual problems of companies in the industrial complex and the aspects that should be supported by the logistics platform. The service design methodology was applied to systematize the procedures for implementing the logistics platform. The feasibility of the established logistics platform was verified through performance indicators and additional satisfaction surveys. This study identified the effectiveness of the systematically established logistics platform through demonstration and suggested policy measures that companies in industrial complexes can effectively utilize. The increasing demand for shared logistics resources and joint logistics centers arises from the challenges faced by companies in aging industrial complexes that predominantly operate independent logistics warehouses and transportation vehicles. Therefore, it is vital for the logistics platform project to enable resident companies to experience tangible benefits, such as cost reduction and operational improvements in logistics. The government needs to continually enhance the development and operation of the logistics platform; in this regard, the implementation procedures and policy recommendations from this dissertation are expected to be helpful. 본 연구는 산업단지 내 기업 간 물류자원 공유의 필요성을 조사하고 체계적인 전략을 통해 정부의 '스마트 물류플랫폼 구축 및 운영사업'의 추진상황을 점검하여 그 성과를 검증하고 효율적인 물류플랫폼 구축을 위한 정책을 제시하는 연구입니다. 산업단지는 제조업 기업이 밀집된 지역으로서 입주기업 간 물류에 중요한 역할을 하고 있습니다. 그러나 20년 이상 된 노후화된 산업단지의 증가와 지속적인 가동률 저하로 고용위기가 발생할 가능성이 있어 우려를 자아내고 있습니다. 이러한 문제를 해결하기 위한 일환으로, 정부는 산업단지내 물류플랫폼 사업을 통해 물류환경을 디지털화하고 산업단지를 저탄소, 고효율, 친환경 지역으로 변화시키는 것을 목표로 '스마트 물류플랫폼 구축 및 운영·사업'을 적극 추진하고 있습니다. 이에 본 연구는 산업단지 내 물류 애로사항을 파악하고 물류플랫폼 사업을 체계적으로 구축하기 위한 방법을 모색하였습니다. 산업단지 내에 물류플랫폼을 도입할 경우 동종산업이나 공급망 체계 내에서 기업 간 시너지 효과가 발생할 것이라는 가설을 중심으로 물류플랫폼의 대상 업종을 선정하기 위해 사전조사를 실시하였습니다. 물류플랫폼의 도입대상은 울산지역의 자동차산업으로 선정하였으며, 물류플랫폼이 제공하는 4가지 서비스인 '공동물류센터', '공동운송서비스', '물류자원공유서비스', '물류정보서비스'에 대한 필요성과 이용의사에 대한 설문조사와 분석을 실시하였습니다. 또한, IPA (Importance-Performance Analysis)를 통해 도입 대상 서비스를 우선적으로 검토하고, 물류단지 내 기업들의 물류운영 애로사항과 애로사항에 대한 설문조사를 실시하였습니다. 추가적으로 물류 전문가 들과의 심층면담을 통해 산업단지 내 기업들의 현실적인 애로사항과 물류플랫폼이 지원해야 할 사항을 분석하였으며, 서비스 설계 방법론을 적용하여 물류플랫폼을 구축하기 위한 절차를 체계화하고, 구축된 물류 플랫폼의 타당성을 성과 지표 및 추가 만족도 조사를 통해 검증하였습니다. 본 연구는 실증을 통하여 체계적으로 구축된 물류 플랫폼의 효과성을 파악하고 산업 단지 내 기업들이 효과적으로 활용할 수 있는 정책 방안을 제시하였습니다. 참고로 공유 물류 자원 및 공동 물류 센터에 대한 수요 증가는 독립 물류 창고 및 운송 차량을 주로 운영하는 노후화된 산업 단지 내 기업들이 직면한 도전 과제에서 발생합니다. 따라서 물류플랫폼 사업은 입주기업들이 물류에 대한 비용절감 및 운영개선 등 가시적인 혜택을 체감할 수 있도록 하는 것이 중요합니다. 정부는 물류플랫폼 개발과 운영을 지속적으로 개선할 필요가 있으며, 이와 관련하여 본 학위논문의 연구과정과 정책적 제언이 도움이 될 것으로 기대합니다.

CRYSTALLIZATION BEHAVIOR OF NEUTRAL Co(III) COMPLEXES WITH CHELATING AMINE LIGAND AND Co(III)-PROMOTED HYDROLYSIS OF AMIDE AND S?S BONDS

Chun, Hyung Phil University of Houston 2000 해외박사

Twenty-one neutral Co(III) complexes whose crystal structures were unknown have been synthesized and characterized by X-ray crystallography in order to investigate their crystallization behavior. Those compounds possess octahedral geometry and include tricyano (1-6), trinitro (7-9), triazido (10-13), trichloro (14), triacetatocobalt(III) (15) and other complexes with mixed anionic ligands (16-21). It has been found that most of the compounds display common patterns in the packing structures and that such patterns are not directly related to their stereochemical environment, such as, facial and meridional configuration, or a local symmetry of chelating amine or anionic ligands. Also, it is shown that a specific intermolecular interaction is not responsible for a structure's being racemic or conglomerate, a phenomenon known as spontaneous resolution of a racemic solution by crystallization. In some cases, the solvation of water molecules and conformational isomerism play a significant role in the crystallization behavior of the compounds. In the second part, crystal structures of various Co(III) complexes obtained by hydrolytic cleavage of amide and S-S bonds are described. In the case of amide hydrolysis, monooxamide (H₂NCOCO₂^-) undergoes hydrolysis by various dichlorocobalt(III) species, and oxalatocobalt(III) complexes are obtained as the products. It is shown, unlike previous belief, that the hydrolysis occurs by cis- or trans-dichlorocobalt(III) complexes and that the mechanism depends on the type of multidentate amine ligand of cobalt. The S-S bonds of polythionates (S_nO_6^(2-), n > 2) are also found to be hydrolyzed by similar cobalt(III) complexes containing triethylenetetramine (trien) or tris-(2-aminoethyl)amine (tren) ligands, but not by bis(ethylenediamine)cobalt(III) complexes. Dithionate (S₂O_6^(2-)) which contains only two sulfur atoms in +5 oxidation state is not hydrolyzed by Co(III) complexes. When the hydrolysis occurs, trithionate (S₃O_6^(2-)) and tetrathionate (S₄O_6^(2-)) commonly give sulfatocobalt(III) complexes, and in case of tetrathionate, pentathionate anion (S_5O_6^(2-)) is generated. The cleavage of S-S bonds in polythionates has only been known to occur in metabolic processes of sulfur bacteria, and such reactions promoted by simple transition-metal complexes are unprecedented.

Structural Variations of Transition Metal Complexes with N,N'-(ethylene-di-p-phenylene)bis(pyridine-2-carboxamide) Ligand and Their Catecholase and Peroxidase Activities : N,N'-(ethylene-di-p-phenylene)bis(pyridine-2-carboxamide)리간드를 가진 전이금속착물의 카테콜과 퍼옥시데이

김오연 경북대학교 대학원 2017 국내석사

단백질의 일차 구조에서 발견 된 Carboxamide그룹은 배위 화학 중요한 리간드 구성 단위이다. 특히, Phenyl-pyridyl-carboxamide를 함유하는 금속 착물들은 비대칭 촉매, 분자 수용기와 Dendrimer 합성에 유용한 것으로 밝혀졌다. 복잡한 구조 및 반응성의 다양성을 조사하기 위해 4자리 리간드인 H2ebpp (= N,N'-(ethylene-di-p-phenylene)bis(pyridine-2-carboxyamide))을 개발하였다. 이 리간드를 이용하여 바나듐, 크롬, 망간, 철, 코발트, 니켈, 구리, 루테늄 같은 다양한 전이금속착물을 합성하였다. 단결정 구조를 통해 다양한 전이금속이온과 산화상태에 따라 다양한 구조가 나타나는 것을 확인하였다. Catecholase는 활성자리에 두 개의 구리이온을 포함하는 tpye-3 단백질로서 산소를 이용하여 catechol을 queinone으로 산화시키는 촉매작용을 한다. 많은 구리착물 모델이 Catecholase activity를 가지는 것으로 보고되고 있다. 최근 구리를 포함하지 않는 금속착물들의 Catecholase activity와 그들의 메커니즘을 규명하려는 연구가 주목받고 있다. 3,5-DTBC (3,5-di-tertbutylcatechol)로 Catecholase activity 실험을 하였을 때 H2ebpp 리간드를 가진 구리, 망간 그리고 코발트 착물들은 기대만큼의 반응성을 가지지 못했다. Perxoidase는 물의 정수, ELISA 연구, 의학 등의 다양한 연구 분야에 활용되고 있다. 그래서 Peroxidase를 모방하는 것은 흥미로운 연구이다. 과거연구에는 Peroxidase activity가 루테늄에서 일어난다는 것을 알려져 있지 않다. 그러나 우리는 루테늄이 Peroxidase에 대해 반응성 보인 것을 확인하였다. Carboxamide group, found in the primary structure of proteins, is an important ligand construction unit for coordination chemistry. Especially, metal complexes containing phenyl-pyridyl-carboxamide groups have been found to be useful in asymmetric catalysis, molecular receptors and dendrimer synthesis. To investigate the diversities of the complex structures and reactivities, we have developed a tetradentate ligand, H2ebpp (= N,N'-(ethylene-di-p-phenylene)bis(pyridine-2-carboxyamide)), to be utilized for synthesizing vanadium, chromium, manganese, iron, cobalt, nickel, copper, and ruthenium complexes. Crystallographic studies of the complexes revealed the variations of the structures from monomeric to dimeric metal complexes depending on the metal ions, their oxidation states and the first coordination spheres. Catecholase (catechol oxidase), catalyzing the oxidation of catechols to the corresponding o-quinones accompanying with the four-electron reduction of O2 to 2H2O, is a type-3 copper protein containing dinuclear copper center. Many model copper complexes have been reported to show catecholase activities. Recent development of non-copper metal complexes with catecholase activities have attracted considerable interests in the catalytic mechanism of catecholase reactions. Among the complexes containing the H2ebpp ligand, copper, manganese and cobalt complexes showed unexpectedly-high catecholase activity when the complexes were treated with 3,5-di-tert-butylcatechol (3,5-DTBC) in the presence of air at basic condition. Perxoidase (peroxide oxidase) is useful for various filed such as water waste, ELISA study, medicine. So it is interesting to mimic peroxidase. It was not known peroxidase activity with ruthenium pervious study. However, we found this activity with ruthenium.

Intramolecular Interactions in Pd(II) Complexes with Various Substituents : A Theoretical Study

아루마렌 경상대학교 대학원 2010 국내석사

In conclusion, this theoretical study reveals various trends in X…X distances in Pd(Ⅱ) complexes upon the variation in terminal ligands. This clearly signifies the major influence of the nature of terminal ligands on the strength of van der Waals X…X interactions. Moreover, a strong correlation between the X…X interactions and charge on X atoms of bridging ligand is also revealed. The A type complexes have exhibited minimum X…X distance in all furan, thiophene, and selenophene bridging oligomers containing complexes. Consequently, it could be concluded that substitution of uncharged terminal ligand may be more helpful to instigate short heteroatom-heteroatom interactions in this motif of Pd(Ⅱ) complexes than charged & uncharged, and charged terminal ligand containing complexes. Moreover, it was also revealed that number of short interactions among heteroatoms in selenophene containing Pd(Ⅱ) complexes were more than those in thiophene and furan containing complexes. While, Pd(Ⅱ) complexes with furan as bridging ligand showed less interactions between heteroatoms than thiophene. This, trend of X…X interactions could be related to the electron-retaining ability of heteroatoms. As the tendency of heteroatom to retain its electron increases, stability of heteroatom…heteroatom interactions decreases. Therefore, furan having most electronegative heteroatom showed weakest interactions and selenophene exhibited the strongest interactions. Thus, another important finding of this research work is that X…X interactions become stronger on going from O to Se. Consequently, in order to instigate short X…X interactions, choice of the appropriate bridging ligand is also an important factor along with the terminal ligands. Therefore, on the basis of these findings, it could be suggested that Pd(Ⅱ) complexes substituted with neutral terminal ligands and having selenophene oligomer as bridging oligomer could be used to activate short X…X interactions in this motif of Pd(Ⅱ) complexes. 헤테로고리 리간드를 가지는 Pd(Ⅱ) 전이금속 화합물들은 컨쥬게이트 리간드에 의해 전기적 및 광학적 성질이 발현되어, 지금까지 매력적인 연구대상으로 각광 받아왔다. 본 연구에서는 헤테로고리 화합물인 furan, thiophene, selenophene들이 가교 리간드 형태로 결합된 가교형 Pd(Ⅱ) 화합물에 연구의 초점을 두었다. Pd(Ⅱ) 화합물에 다양한 형태의 말단 리간드를 도입하여 계산하였으며, 또한 두 가교 리간드의 헤테로 원자들 사이의 상호 작용(O…O, S…S, Se…Se)에 의한 구조적 변화를 조사하였다. Pd는 LANL2DZ, 다른 원자는 3-21g*, 6-31g*의 기저함수를 사용하였으며, 계산 방법은 밀도범함수 이론 (DFT)를 사용하여 최적화하였다. 원자들의 전하는 NBO 방법을 사용하여 원자들의 전하 분포를 조사하였다. Pd(Ⅱ) 화합물의 경우, 말단 리간드의 종류에 따른 1) 양쪽에 전하가 없는 말단 리간드를 갖는 A 화합물, 2) 전하가 있는 것과 전하가 없는 말단 리간드를 갖는 B 화합물, 3) 양쪽 모두 전하가 있는 말단 리간드를 갖는 C 화합물들로 분류하였다. 또한, 중심 금속에서 말단 리간드의 환경 변화에 따른 영향과 Pd(Ⅱ) 화합물에서의 가교 리간드의 기하학적 구조를 자세히 조사하였다. 이러한 연구 결과, 중성 말단 리간드를 갖는 A 화합물들은 다른 화합물들에 비해 가교 리간드의 헤테로 원자 사이에 강한 상호 작용을 나타내었다. selenophene를 갖는 Pd(Ⅱ) 화합물이 thiophene, furan를 갖는 화합물보다 분자내 상호작용을 더 잘하는 것으로 밝혀졌다.