• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.796-800
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• 2004

The structure of [Cu(tpen)]$(ClO_4)_2$ (tpen = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethanediamine) has been identified by X-ray crystallography. The copper(II) ion is surrounded by two amine N atoms and three pyridine N atoms of the ligand, making a distorted trigonal-bipyramid. Among the six potential N donor atoms (two amine N and four pyridine N atoms), only one pyridine N atom remains uncoordinated. We examined structural changes on addition of $Cl^-$ to $[Cu(tpen)]^{2+}$(1). The addition of $Cl^-$ in methanol resulted in the formation of a novel dinuclear copper(II) complex $[Cu_2Cl_2(tpen)](ClO_4)_2{\cdot}H_2O$. The structure of the dinuclear complex was verified by X-ray crystallography. Each copper(II) ion in the dinuclear complex showed a distorted square planar geometry with two pyridine N atoms, one amine N atom and one $Cl^-$ ion.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.1037-1040
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• 2011

The dinuclear complex 1 with cooperative hydrogen bonds can be prepared by the metal-directed reaction of Eq. (2). This work shows that the coordinated hydroxyl group trans to the secondary amino group is deprotonated more readily than that trans to the tertiary amino group and acts as the hydrogen-bond accepter. The lattice water molecules in 1 act as bridges between the two mononuclear units through hydrogen bonds. The complex is quite stable as the dimeric form even in various polar solvents. The complex exhibits a weak antiferromagnetic interaction between the metal ions in spite of relatively long Cu$\cdots$Cu distance. This strongly supports the suggestion that the antiferromagnetic behavior is closely related to the cooperative hydrogen bonds.

• 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.

• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1803-1806
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• 2008

• 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.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.

• Bulletin of the Korean Chemical Society
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• v.27 no.3
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• pp.435-438
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• 2006

• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.3017-3020
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• 2010

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4231-4234
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• 2012

• Bulletin of the Korean Chemical Society
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• v.20 no.4
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• pp.491-493
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• 1999