• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.1012-1019
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• 2004

The synthesis of novel group 9 metal complexes containing the S,S'-chelate ligands, $Li_2S_2C_2B_{10}H_{10}$ (2a) and $LiS(S=PMe_2)C_2B_{10}H_{10$} (2b), is described. Two new dinuclear complexes of the type $[{(cod)M}_2(S,S'-S_2C_2B_{10}H_{10})]$ (cod = 1,5-cyclooctadiene; M = Rh (3a), or Ir (3b)) were synthesized by the reaction of chloridebridged dimers $[M({\mu}-Cl)(cod)]_2$ with one molar equivalent of the corresponding dilithium dithiolato ligand $Li_2S_2C_2B_{10}H_{10}$ (2a). X-ray crystal structure analysis of 3a revealed a dinuclear structure in which each (cod)Rh unit is attached to a distinct sulfur atom of a 1,2-dithio-o-carboranyl ligand (2a). Additionally, the electrochemical properties of 3a and 3b were investigated by cyclic voltammetry. In an analogous manner, reaction of the lithium dithiolato ligand $LiS(S=PMe_2)C_2B_{10}H_{10}$ (2b) with $Cp^{\ast}CoI_2(CO)$ produced a mononuclear dithiolato complex, $[Cp^{\ast}CoI{(S,S'-S(S=PMe_2)C_2B_{10}H_{10})}]$ (4), which was characterized by single-crystal X-ray analysis.

• Bulletin of the Korean Chemical Society
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• v.34 no.3
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• pp.725-730
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• 2013

An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles $L^1-L^3$ ($L^1$: 20-membered $O_3S_2$, $L^2$: 20-membered $O_2S_3$, and $L^3$: 23-membered $O_4S_2$) with $d^{10}$-metal ($Ag^+$, $Hg^{2+}$, and $Pb^{2+}$) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of $L^2$ and $L^3$ with the silver(I) salts ($PF_6{^-}$ and $SCN^-$) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex $[Ag_2(L^2)_2](PF_6)_2{\cdot}3CH_2Cl_2$ (1) and a linear dinuclear complex $[Ag_2(L^3)_2(SCN)_2]$ (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of $L^1$ and $L^2$ with mercury(II) salts ($SCN^-$ and $Cl^-$) gave a mononuclear 1:1 complexes $[Hg(L^1)(SCN)_2]$ (3) and $[Hg(L^2)Cl_2]$ (4) with anion coordination in both cases. $L^2$ reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex $[Pb(L^2)_2(ClO_4)_2]$ (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anioncoordination ability on the resulting topologies of the soft metal complexes are discussed.

• Polymer(Korea)
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• v.30 no.1
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• pp.64-69
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• 2006

A series of dinuclear half-sandwich titanium complexes with aryloxy substituent at titanium$[(\eta^5-cyclopentadienyl)(aryloxy)TiCl_2]_2[(CH_2)_n]$ (n=3, n=6, n=9) have been successfully synthesized and their styrene polymerization properties have been investigated. All complexes are characterized by $^1H\;NMR,\;^{13}C\;NMR$, elemental analysis, and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has beer conducted in the presence of MMAO. It was found that (i) all the prepared complexes were very effective catalyst for the production of SPS (syndiotactic polystyrene), (ii) the complex with the longest bridge between the two active sites exhibited greatest catalytic activity among the three catalysts, but produced SPS with the smallest molecular weight, (iii) the activities of dinuclear half-titanocens with aryloxy substitution at titanium metal were greater than those of the chloride substituted compounds. These results indicate that not only the nature of the bridge between the two active sites but also the property of substituents at the metal exert a significant influence on the polymerization behaviors of the dinuclear half-titanocene.

• Rapid Communication in Photoscience
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• v.3 no.3
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• pp.42-47
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• 2014

Development of molecular and supramolecular systems showing efficient photoinduced energy or electron transfer are of current research interest due to their applications in various chemical and biological processes. Various polypyridine metal complexes including Ru(II), Ru(III), Os(II), Pt(II), Fe(II), Re(I), Ir(III) and so on as a metal center introduce for expanding some more understanding of molecular-scale photoelectronics. Their complexes are concisely classified by the types of relay ligands as follows; (a) metal-direct ligand-metal system; dinuclear or trinuclear systems, (b) metal-nonconjugated ligand-metal system and metal-nonconjugated ligand system having flexible/rigid ligand, (c) metal-conjugated ligand-metal system, and (d) conjugated ligand-metal-conjugated ligand system and metal-self assembly ligand-metal system. It is pointed out that the role played by the relay ligands is important in constructing the metal complexes.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.618-622
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• 1997

The polysiloxane-bridged dinuclear metallocenes $[(SiMe_2O)_n-SiMe_2(C_5H_4)_2][(C_9H_7)ZrCl_2]_2$ (n=1 (7), 2 (8), 3 (9)) have been generated as a model complex for the immobilized metallocene at silica surface by treating the respective disodium salts of the ligands with 2 equivalents of $(C_9H_7)ZrCl_3$ in THF. All three complexes are characterized by $^1H$ NMR and measurement of metal content through ICP-MS. It turned out that the values of ${\Delta}{\delta}=[{\delta}_d-{\delta}_p]$, the chemical shift difference between the distal $({\delta}_d)$ and proximal $({\delta}_p)$ protons, for the produced dinuclear compounds (0.47 for 7, 0.49 for 8, and 0.5 for 9) were larger than the Δδ value of the known ansa-type complex holding the same ligand as a chelating one, that is just the opposite to the normal trend. In order to compare polymerization behavior of the dinuclear metallocene with the corresponding mononuclear metallocene, (Cp)$(C_9H_7)ZrCl_2$ was separately prepared. To investigate the catalytic properties of the dinuclear complexes and mononuclear metallocenes ethylene polymerization has been conducted in the presence of MMAO. The polymerization results display the typical activity dependence on polymerization temperature for all complexes. The most important feature is that the polymers from the dinuclear metallocenes represent enormously improved molecular weight compared with the polymer from the corresponding mononuclear metallocene. In addition, the influence of the nature of the bridging ligand upon the reactivities of the dinuclear metallocenes has also been observed.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.556-559
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• 1992

Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M= Rh, Ir) reacts rapidly with 1,4-dicyanobenzene or 1,4-dicyano-2-butene to yield dinuclear metal complexes $[(PPh_3)_2(CO)M({\mu}-dicyanobenzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M = Rh; II: M = Ir) or $[(PPh_3)_2(CO)M({\mu}-dicyano-2-benzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (III: M = Rh; IV: M = Ir), respectively. Compounds I, II, III, and IV were characterized by $^1H$-NMR, $^{31}P$-NMR, and infrared spectrum. Dichloromethane solution of II and IV reacts with $H_2\;and\;I_2$ to yield oxidative addition complexes $[(PPh_3)_2(CO)IrX_2({\mu}-E)X_2Ir(CO)(PPh_3)_2](SO_3CF_3)_2$ (V; E = 1,4-dicyanobenzene, $X_2$ = $H_2$; VI : E = 1,4-dicyano-2-butene, $X_2$ = $H_2$; VII; E = 1,4-dicyanobenzene, $X_2$ = $I_2$). All metal complexes are bridged by the cyanide groups. Compounds Ⅴ, Ⅵ, and Ⅶ are characterized by conventional methods.

• Bulletin of the Korean Chemical Society
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• v.13 no.2
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• pp.158-162
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• 1992

Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3(M=Rh$, Ir)reacts rapidly with Pyrazine or 4,4'-bipyridyl to yield dinuclear metal complexes $[(PPh_3)_3(CO)M({\mu}-pyrazine)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M= RhH; III: M=Ir) or [$(PPh_3)_2$(CO)M(${\mu}$-44'-bipyridyl)M(CO)$(PPh_3)_2](SO_3CF_3)_2$, (II: M=Rh; IV: M=Ir), respectively. Compounds, I, II, III, and IV were characterized by $^1H-NMR$, $^{13}C-NMR$, $^{31}P-NMR$, and infrared spectrum. Ethanol solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M=Rh, Ir) also reacts with $(TBA)_2$M'$(CN)_4$ (M'=Pd, Pt) to yield trinuclear metal complexes [$(PPh_3)_2$(CO)dM-NCM'$(CN)_2$CN-M(CO)$(PPh_3)_2]$ (V : M=Rh, M'=Pd; VI : M=Rh, M'=Pt; VII: M=Ir, M'=Pd; VIII: M=Ir, M'=Pt). The trinuclear metal complexes V, VI, VII, and VIII are bridged by the cyanide groups. The infrared spectrum of V, VI, VII, and VIII supports the presence of the bridged cyanide and terminal cyanide group.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.331-334
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• 1996

New copper(Ⅱ) complex of the pentaaza non-macrocyclic ligand 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl)-1,3-diazacyclohexane (2) and a dinuclear copper(Ⅱ) compex of the bis(macrocyclic) ligand 3, in which two 1,5,8,10,12,15-hexaazabicyclo[11.3.11.5]heptadecane subunits are linked together by an ethylene chain through the uncoordinated nitrogen (N10) atoms, have been prepared selectively by the reaction of the metal ion, 1,4,8-triazaoctane, ethylenediamine, and formaldehyde. The dinuclear complex [Cu2(3)]4+ has been also prepared by the reaction of [Cu(2)]2+ with ethylenediamine and formaldehyde. The reaction products largely depend on the molar ratio of the reactants employed. The mononuclear complex or each macrocyclic subunit of the dinuclear complex contains one 1,3-diazacyclohexane ring and has a square-planar geometry with a 5-6-5 or 5-6-5-6 chelate ring sequence. In acidic solution, the copper(Ⅱ) complex of 2 dissociates more slowly than those of other related non-cyclic polyamines.

• Polymer(Korea)
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• v.24 no.2
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• pp.159-167
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• 2000

The polymethylene-bridged dinuclear half-titanocenes [(CH$_2$)$_{n}$(C$_{5}$ H$_4$)$_2$][TiCl$_3$]$_2$ (n=5(10), 7(11), 9(12)) have been synthesized by treating the distannylated derivatives of the ligands with two equivalents of TiCl$_4$ in toluene. All complexes are characterized by IR, $^1$H NMR, $^{13}$ C NMR and mass spectrometry. In order to examine the catalytic properties of the dinuclear complexes styrene polymerization has been conducted in the presence of MMAO. From the polymerization experiments it was found that ( i ) all the prepared complexes 10-12 produced syndiotactic polystyrenes, ( ii ) the complex 12 holding the longest bridging ligand exhibited the highest activity but produced a polymer having the smallest molecular weight among the polymethylene-bridged dinuclear half-titanocenes. This behavior was attributed to the influence of electron-donating caused by the polymethylene bridge between two active centers as well as the effect of steric congestion around metal center caused by the proximal distance between two active sites.s.

• Journal of the Korean Chemical Society
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• v.38 no.7
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• pp.485-495
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• 1994

Several new symmetric and asymmetric homo and hetero dinuclear complexes of the type $[Cl(dppp)(NO)_2M({\mu}-pyz)M'(NO)_2(dppp)Cl][ClO_4]_2$ and $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(dppp)Cl][ClO_4]_2$(M,M'= Mo or W; phen = 1,10-phenanthroline; dppp = 1,3-bis(diphenylphosphino)propane; pyz = 1,4-pyrazine) were synthesized in three-steps starting from $[M(NO)_2Cl_2]_n(M = Mo, W)$. The final products were purified by eluting it through silica gel column ($2{\times}20$ cm) with acetone as the eluent. Characterization of these complexes and some related complexes was accomplished through UV-vis., $^1H$-NMR, $^{13}C$-NMR and IR spectroscopies as well as elemental analysis. The infrared spectra indicate that the NO groups occupy cis-positions of the octahedral. The $^1H$ and $^{13}C-NMR$ data for the new compounds revealed a dimeric structures with bridged pyz.