• Bulletin of the Korean Chemical Society
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• v.19 no.11
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• pp.1207-1210
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• 1998

The diamagnetic six-coordinate ruthenium polypyridyl complexes have been prepared and assigned. 1H NMR spectral studies were used to unravel the ligand field strength and the basicity on the chemical shift to the particular proton of ligand L in [(tpy)(L)RuⅡ(X)]+/2+ (L=bpy, bqi, dmbpy, phen; X=Cl, CN, N3, NCCD3, NO2, SCN) complexes.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.11a
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• pp.192-195
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• 2003

There has been increasing interest in the applications of synthesized molecules of nanometer scale in recent years due to their potential utilization in various fields such as biology, optoelectronics and molecular electronics. In this study, the terpyridine-platinum (II) complex on the periphery of the dendritic carbosilane has been prepared from the reaction of Pt(COD)Cl2 and the 4'-functionalized-(2,2':6',2"-terpyridine) on dendrimers. The self-assembly process was carried out to obtain indivially dispersed dendrimer on Au (111) substrate. It was found that STM was unsuitable to obtain a obvious image of dendrimers. Tapping-mode atomic force microscopy(AFM) has been used to investigate the shape and size of dendrimers individually dispersed on Au (111)substrate. As a result, the imaged single dendrimer show that dendrimer is dome shaped and its size can be measured by tapping-mode AFM.

• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.619-624
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• 1995

Oxidation of triphenylphosphine to triphenylphosphine oxide by [(tpy)(bpy)Ru(O)]2+ (tpy is 2,2':6',2"-terpyridine and bpy is 2,2'-bipyridine) in CH3CN has been studied. Experiments with the 18O-labeled oxo complex show that transfer of oxygen from [(tpy)(bpy)RuⅣ=O]2+ to triphenylphosphine is quantitative within experimental error. The reaction is first order in each reactant with k (25.3 ℃)=1.25 × 106 M-1s-1. The inital product, [(tpy)(bpy)RuⅡ-OPPh3]2+, is formed as an observable intermediate and undergoes slow k (25 ℃)=6.7 × 10-5 s-1 solvolysis. Activation parameters for the oxidation step are ΔH≠=3.5 kcal/mol and ΔS≠=-23 eu. The geometry at ruthenium in the complex cation, [(tpy)(bpy)RuⅡ(OH2)]2+, is approximately octahedral with the ligating atoms being the three N atoms of the tpy ligand, the two N atoms of the bpy ligand, and the oxygen atom of the aqua ligand. The Ru-O bond length is 2.136(5) Å.

• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.75-80
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• 1997

Preparation and properties of Eu(hfa)3·L (Hhfa = hexafluoroacetylacetone, L = bis(2-methoxyethyl)ether, diglyme, and 2, 2':6', 2"-terpyridine, tpy), which are potential CVD precursors for europium, were investigated. The reaction of the Eu2O3 with Hhfa in the presence of tridentate neutral ligand yielded the nine-coordinated Eu(hfa)3·L. Eu(hfa)3·diglyme is air- and moisture-stable and most importantly has good volatility and thermal stability. Eu(hfa)3·tpy shows no sublime intact. The complex Eu(hfa)3·diglyme has been characterized by an X-ray structure determination; monoclinic P21/n, a=10.252(1), b=16.051(6), c=19.392(8) Å, β=96.10(2)°, V=3173(2) Å3. The europium atom in Eu(hfa)3·diglyme adopts a square-antiprismatic geometry with the ninth coordinating oxygen atom capping one of the square faces. All the adducts have been characterized by IR, TGA/DTA.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2139-2152
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• 2007

Ruthenium complex-catalyzed reactions often require highly qualified tuning of reaction conditions with substrates to attain high yield and selectivity of the products. In this review, our strategies for achieving characteristic ruthenium complex-catalyzed co-oligomerization of different alkenes are disclosed: 1) The codimerization of 2-norbornenes with acrylic compounds by new ruthenium catalyst systems of RuCl3(tpy)/Zn [tpy = 2,2':6',2''-terpyridine] or [RuCl2(η6-C6H6)]2/Zn in alcohols, 2) A novel synthesis of 2-alkylidenetetrahydrofurans from dihydrofurans and acrylates by zerovalent ruthenium catalysts, such as Ru(η4-cod)(η6-cot) [cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene] and Ru(η6-cot)(η2-dmfm)2 [dmfm = dimethyl fumarate], 3) Regio- and stereoselective synthesis of enamides by Ru(η6-cot)(η2-dmfm)2-catalyzed codimerization of N-vinylamides with alkenes, and 4) Unusual head-to-head dimerization of styrenes and linear codimerization of styrenes with ethylene by Ru(η6-cot)(η2-dmfm)2 catalyst in the presence of primary alcohols.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Bulletin of the Korean Chemical Society
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• v.32 no.spc8
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• pp.3003-3008
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• 2011

Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

• Rapid Communication in Photoscience
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• v.4 no.1
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• pp.22-24
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• 2015

A new trinuclear complex $[Ru(TPrPc)(CO)]_2[Ru(pytpy)_2](PF_6)_2$ (TPrPc = 2,7,12,17-tetra-n-propylporphycenato dianion and pytpy = 4'-(4-pyridyl)-2,2':6',2"-terpyridine) has been synthesized and characterized as the first example of a discrete molecular wire containing metalloporohycenes as a building block. The trinuclear complex shows multiple-step redox behavior in 0.1 M n-$Bu_4NPF_6$-dichloromethane. The mononuclear $[Ru(pytpy)_2]^{2+}$ precursor shows emission at 640 nm (deaerated acetone, 298 K) upon illumination at the metal-to-ligand charge transfer (MLCT) band at 495 nm, but the trinuclear molecular wire is found to be non-emissive upon photoexcitation at the central $[Ru(pytpy)_2]^{2+}$ entity, indicating an efficient quenching ability of the axially-linked, ruthenium(II)-porphycene chromophores in an intramolecular fashion.

• Archives of Pharmacal Research
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• v.29 no.12
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• pp.1091-1095
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• 2006

For the development of novel antitumor agents, we designed and synthesized terpyridines, and their biological activities were evaluated. Although most of the newly prepared terpyridines showed strong cytotoxicity against several human cancer cell lines, [2,2';6',2"]-terpyridine displayed the most significant cytotoxicity.