• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2684-2688
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• 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.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2544-2548
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• 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
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• v.33 no.5
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• pp.1675-1680
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• 2012

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2203-2206
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• 2013

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4197-4200
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• 2012

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1581-1585
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• 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 $J=-0.084(3)cm^{-1}$.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.2075-2077
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• 2005

• 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.

• Analytical Science and Technology
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• v.21 no.6
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• pp.562-568
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• 2008

A novel two-dimensional cadmium(II)-nickel(II) bimetallic host clathrate, $[Cd{NH_2CH_2CH_2OH}_2Ni(CN)_4]{\cdot}3C_6H_5NH_2{\cdot}H_2O$, 1, has been synthesized and structurally characterized by X-ray single crystallographic method. The clathrate 1 crystallizes in the monoclinic system, space group $P2_1/c$ with a = 14.370(3), b = 7.728(1), c = 28.172(4) ${\AA}$, ${\beta}=97.58(1)^{\circ}$, V = 3101.1(9) ${\AA}^3$, Z = 4. The host framework of the clathrate 1 is built of the cyanide bridges between octahedral Cd(II) atom and square planar Ni(II) atom. The octahedral Cd atoms ligated by two 2-aminoethanol molecules and four cyanide ligands bridged with square planar Ni atoms. The Ni atoms bridges to four Cd atoms via cyanides is made up of puckered quadrangles of composition $\{CdNi(CN)_2\}_2$, all edges are shared. This cyanide bridges form an infinite two-dimensional host networks stacking along b axis. 2-Aminoethanol ligands bond to Cd atom through N atom as a monodentate ligand in the axial position and four cyanides take an equatorial plane with all in trans-configurations. The aniline guest molecules and water molecules are located in between the host layer sheets, respectively.

• Journal of Environmental Science International
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• v.3 no.4
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• pp.439-443
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• 1994

In aqueous acid solution ${[Cr(CN)_6]}^{3-}$ aquates via a series of stepwise stereospecific reactions to give ${[Cr{(H_2O)}_6]}^{3+}$as the final product.Some of the intermediate cyanoaquo complexes in the sequence have been isolated.These complexes aquate by both acid independent and acid denpendent pathways, the latter involving protonation of the cyano ligands followed by aquation of the singly protonated species. The kinetic data for the aquation of {[CrCN{(H_2O)}_5]}^{2+}$ are consistent with the transition state structure ${[{(H_2O)}_4Cr(CN)-OH-Cr{(H_2O)}_5]}^{3+}$. Addition of $Cr^{2+}$ to solutions of cyanocobalt(III) complexes produces the metastable intermediate${[CrNC{(H_2O)}_5]}^{2+}$ This isomerizes to in a $Cr^{2+}$-catalyzed reaction which occurs by a ligand-bridged electron-change mechnism. From acid catalysis on these aquation reactions, it product HCN. Especially, $HSO_3$-ions do the role of catalyst in the formation of HCN from $CrCN^{3-}$