• Bulletin of the Korean Chemical Society
• /
• 제20권10호
• /
• pp.1115-1117
• /
• 1999

• Bulletin of the Korean Chemical Society
• /
• 제32권8호
• /
• pp.2544-2548
• /
• 2011

Two pyridinecarboxamide cobalt dicyanide building blocks and Mn(III) compounds have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three trinuclear cyanide-bridged $Co^{III}-Mn^{II}$ complexes: $\{[Mn(MeOH)_4][Co(bpb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (1), $\{[Mn(MeOH)_4][Co(bpmb)(CN)_2]_2\}{\cdot}2MeOH{\cdot}2H_2O$ (2) and $\{[Mn(DMF)_2(en)_2][Co(bpb)(CN)_2]_2\}{\cdot}2DMF{\cdot}H_2O$ (3) ($bpb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, en = ethylenediamine). Single crystal X-ray diffraction analysis shows their similar sandwich-like structures, in which the two cyanide-containing building blocks act as monodentate ligands through one of their two cyanide groups to coordinate the Mn(II) center. For complex 3, it was further linked into one-dimensional structure by ethylenediamine acting as bridges. Investigation of the magnetic properties of complex 3 reveals weak antiferromagnetic coupling between the neighboring Mn(II) centers through the bridging ethylenediamine molecule. A best-fit to the magnetic susceptibilities of complex 3 gave the magnetic coupling constant J = -0.073(2) $cm^{-1}$.

• Bulletin of the Korean Chemical Society
• /
• 제35권9호
• /
• pp.2684-2688
• /
• 2014

Two two-dimensional cyanide- and phenoxo-bridged heterometallic M(II)-Mn(III) (M = Ni, Pd) coordination polymers $\{[Mn(saltmen)]_4[Ni(CN)_4]\}(ClO_4)_2{\cdot}CH_3OH{\cdot}H_2O$ (1) and $\{[Mn(saltmen)]_4[Pd(CN)_4]\}(ClO_4)_2{\cdot}CH_3CN{\cdot}H_2O$ (2) ($saltmen^{2-}$ = N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato)dianion) have been obtained by using $K_2[M(CN)_4]$ as building blocks and a salen-tpye Schiff-base manganese(III) compound as assembling segment. Single X-ray analysis reveals their isostrutural cyanide-bridged $MMn_4$ pentanuclear cationic structure. The four Schiff base manganese units of the pentanuclear entity are self-complementary through the phenoxo oxygen atoms from the neighboring complex, therefore forming cyanide- and phenoxo-bridged 2D sheet-like structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Mn(III) ions bridged by the phenoxo oxygen atoms with J = 2.13 and $2.21cm^{-1}$ for complexes 1 and 2, respectively.

• 공업화학
• /
• 제18권6호
• /
• pp.630-635
• /
• 2007

구조중에 1개의 tert-부틸기를 가진 새로운 형태의 키랄살렌 착체를 합성하여 비대칭반응 촉매로서 활용하였다. 알루미늄족의 금속염을 소유한 이량체형의 키랄 살렌 촉매는 에폭사이드의 산소고리를 페놀류로 여는 비대칭반응에서 매우 높은 활성과 선택성을 나타내었다. 또한 무기담체에 고정화된 살렌 착체도 이 반응에 대하여 효과적인 촉매로 사용할 수 있었다. 새로운 키랄 살렌촉매 중에 존재하는 금속염의 종류는 광학선택적 반응에서 중요한 영향을 나타내었다.

• Bulletin of the Korean Chemical Society
• /
• 제14권1호
• /
• pp.137-143
• /
• 1993

The tetranuclear heterometallic complex CpMo$Os_3(CO)_{10}({\mu]-H)2[{\mu}3-{\eta}^2-C(O)CH_2Tol]\;(1,\;Cp={\eta}^5-C_5H_5,\;Tol=p-C_6H_4Me)$ has been examined by variable-temperature $^{13}$C-NMR spectroscopy and by a full three-dimensional X-ray structual analysis. Complex 1 crystallizes in the orthorhombic space group Pna2$_1$ with a = 12.960(1) ${\AA}$, b = 11.255(l) ${\AA}$, c = 38.569(10)${\AA}$, V = 5626(2) ${\AA}^3$ and ${\rho}$(calcd) = 2.71 gcm$^{-3}$ for Z = 8 and molecular weight 1146.9. Diffraction data were collectedon a CAD4 diffractometer, and the structure was refined to $R_F$ = 9.7% and $R_{W^F}$ = 9.9% for 2530 data (MoK${\alpha}$ radiation). There are two essentially equivalent molecules in the crystallographic asymmetric unit. The tetranuclear molecule contains a triangulated rhomboidal arrangement of metal atoms with Os(2) and Mo at the two bridgehead positions. The metal framework is planar; the dihedral angle between Os(l)-Os(2)-Mo and Os(3)-Os(2)-Mo planes is 180$^{\circ}$. A triply bridging (${\mu}_3,\;{\eta}^2$) acyl ligand lies above the Os(l)-Os(2)-Mo plane; the oxygen atom spans the two bridgehead positions, while the carbon atom spans one bridgehead position and an acute apical position. The molecular architecture is completed by an ${\eta}^5$-cyclopentadienyl ligand and a semi-triply bridging carbonyl ligand on the molybdenum atom, and nine terminal carbonyl ligands-four on Os(3), three on Os(l), and two on Os(2). The two hydride ligands are inferred to occupy the Os(l)-Os(2) and Mo-Os(3) edges from structural and NMR data.

• Bulletin of the Korean Chemical Society
• /
• 제33권5호
• /
• pp.1581-1585
• /
• 2012

Two pyridinecarboxamide dicyanidecobalt(III) building blocks and two mononuclear seven-coordinated macrocycle manganese(II) compounds have been rationally selected to assemble cyanide-bridged heterobimetallic complexes, resulting in three cyanide-bridged $Co^{III}-Mn^{II}$ complexes. Single X-ray diffraction analysis show that these complexes $\{[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}CH_3OH{\cdot}0.5H_2O$ ($\mathbf{1}$), $\{[Mn(L^2)][Co(bpb)]\}ClO_4{\cdot}0.5CH_3OH$ ($\mathbf{2}$) and ${[Mn(L^1)][Co(bpb)]\}ClO_4{\cdot}H_2O$ ($\mathbf{3}$) ($L^1$ = 3,6-diazaoctane-1,8-diamine, $L^2$ = 3,6-dioxaoctano-1,8-diamine; $bpb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)benzenate, $bpmb2^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate) all present predictable one-dimensional single chain structures. The molecular structures of these one-dimensional complexes consists of alternating units of $[Mn(L)]^{2+}$ ($L=L^1$ or $L^2$) and $[Co(L^{\prime})(CN)2]^-$ ($L^{\prime}=bpb2^{2-}$, or $bpmb2^{2-}$), forming a cyanide-bridged cationic polymeric chain with free $ClO_4{^-}$ as the balance anion. The coordination geometry of manganese(II) ion in the three one-dimensional complexes is a slightly distorted pentagonal-bipyrimidal with two cyanide nitrogen atoms at the trans positions and $N_5$ or $N_3O_2$ coordinating mode at the equatorial plane from ligand $L^1$ or $L^2$. Investigation over magnetic properties of these complexes reveals that the very weak magnetic coupling between neighboring Mn(II) ions connected by the diamagnetic dicyanidecobalt(III) building block. A best-fit to the magnetic susceptibility of complex ${\mathbf}{1}$ leads to the magnetic coupling constants $J=-0.084(3)cm^{-1}$.