• Bulletin of the Korean Chemical Society
• /
• v.23 no.6
• /
• pp.824-829
• /
• 2002

New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.7
• /
• pp.1044-1050
• /
• 2005

The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.5
• /
• pp.561-567
• /
• 1993

The twelve macrocycle (L) complexes of cadmium(II) nitrate have been synthesized: $CdL(NO_3)_2$. All the complexes have been indentified by elemental analysis, electric conductivity measurements, IR and NMR spectroscopic techniques. The molar electric conductivities of the complexes in water and acetonitrile solvent were in the range of 236.8-296.1 $cm^2{\cdot}mol^{-1}{\cdot}ohm^{-1}$ at 25$^{\circ}$C. The characteristic peaks of macrocycles affected from Cd(II) were shifted to lower frequencies as compared with uncomplexed macrocycles. A complex with 1,4,8,11-tetrakis(methylacetato)-1,4,8,11-tetraaza cyclodecane (L4) exhibited two characteristic bands such as strong stretching (1646 $cm^{-1})$, and weaker symmetric stretching band (1384 $cm^{-1})$. NMR studies indicated that all nitrogen donor atoms of macrocycles have greater affinity to cadmium(II) metal ion than do the oxygen atoms. The $^{13}$C-resonance lines of methylene groups neighboring the donor atom such as N and S were shifted to a direction of high magnetic field and the order of chemical shifts were $L_1 < L_2 < L_3 < L_6 < L_4$. Also the chemical shifts values were larger than those of methylene groups bridgeheaded in side-armed groups. This result seems due to not only the strong interaction of Cd(Ⅱ) with nitrogen donors according to the HSAB theory, but weak interaction of Cd(Ⅱ) and COO- ions or sulfur which is enhanced by the flexible methylene spacing group in side-armed groups. Thus, each additional gem-methyl pairs of L_3, L_4\;and\; L_6$ macrocycles relative to $L_1, L_2,\;and\;L_5$ leads to an large enhancement in Cd(II) affinity. ^{13}C$-NMR spectrum of the complex with $L_{12}$ (1,5,9,13-tetracyclothiacyclohexadecane-3,11-diol) reveals the presence of two sets of three resonance lines, and intensities of the each resonance line have the ratio of 1 : 2 : 2. This molecular conformation is predicted as structure of tetragonal complex to be formed by coordinating two sulfur atoms and the other two sulfur atoms which is affected by OH-groups.