Zinc-Containing Carboxylate-Bridged Heterodimetallic Complexes and Their Reactions with Phosphodiester Ligands
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- 作者：Tomoaki Tanase ; Joanne W. Yun ; and Stephen J. Lippard
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：June 5, 1996
- 年：1996
- 卷：35
- 期：12
- 页码：3585 - 3594
- 全文大小：540K
- 年卷期：v.35,no.12(June 5, 1996)
- ISSN：1520-510X
文摘
A series of zinc-containing heterodimetallic complexes wereprepared by using the dinucleating ligand XDK[H2XDK = m-xylylenediaminebis(Kemp's triacid imide)]. Mononuclear[Zn(XDK)(H2O)] (1) reacts with1equiv of M(acac)2·2H2O (acac =2,4-pentanedionate) to afford the heterodimetalliccompounds[ZnIIMII(XDK)(acac)2(CH3OH)2]·H2O(2·H2O, M = Co, 65% isolated yield;3·H2O, M = Mn, 54%;4·H2O, M= Fe, 30%; 5·H2O, M = Ni, 32%). Asdetermined by X-ray crystallography, 2-5 eachcontain a ZnIIMII dinuclearcore bridged by XDK and acac ligands. The zinc and M atoms havetrigonal bipyramidal and octahedral geometries,respectively. The Zn···M separations depend on the metal ionin the octahedral site (2, M = Co, 3.440(2) Å;3,M = Mn, 3.517(1) Å; 4, M = Fe, 3.492(1) Å;5, M = Ni, 3.397(1) Å), a variation which iscorrelated with theionic radius of the high-spin octahedral metal ion. The reactionof 2 with diphenyl hydrogen phosphate affordedthe bis(phosphate) complex[ZnCo(XDK){
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2-(PhO)2PO2}{1-(PhO)2PO2}(CH3OH)2(H2O)](7, 49% yield). TheZnCo center is bridged by the XDK through its two carboxylate groupsand by a diphenyl phosphate ligand. Theother diphenyl phosphate is terminally coordinated to the zinc atom ina monodentate fashion. The Zn···Cointeratomic distance is 3.846(1) Å. An analogousbis(phosphate) homodinuclear complex,[Zn2(XDK){-2-(PhO)2PO2}{1-(PhO)2PO2}(CH3OH)2(H2O)](8), was prepared by reacting[Zn2(XDK)(acac)2(CH3OH)2](6) withdiphenyl hydrogen phosphate in 64% yield. Compound 8,which is isomorphous with 7, has anasymmetricaldizinc core bridged by XDK and a phosphate ligand (Zn···Zn= 3.869(2) Å). The monodentate diphenylphosphateligand dissociates from the dimetallic center of 8 insolution, as revealed by molar conductivity and 1Hand31P{1H} NMR spectroscopic studies.The resulting free phosphate ligand exchanges with the bridgingone inmethanol-d4. The present results provide auseful synthetic route to carboxylate-bridgedheterodimetalliccompounds, which are potential models for the active centers innonredox metalloproteins. Crystal data are asfollows. 2: monoclinic,P21/c, a =17.725(7) Å, b = 12.354(4) Å, c =21.815(6) Å, 
= 90.45(3)
, V =4777(2)Å3, Z = 4; R = 0.049 andRw = 0.051 for 3884 reflections withI > 3
(I). 3: monoclinic,P21/c, a =17.292(2)Å, b = 12.450(1) Å, c = 21.717(2)Å, = 91.464(7), V = 4673.9(7)Å3, Z = 4; R = 0.046 andRw = 0.051 for3876 reflections. 4: monoclinic,P21/c, a =17.630(1) Å, b = 12.374(2) Å, c =21.771(2) Å, = 90.306(8),V = 4749.4(7) Å3, Z = 4;R = 0.041 and Rw = 0.049 for 3248reflections. 5: monoclinic,P21/c, a =17.817(2)Å, b = 12.241(3) Å, c = 21.786(2)Å, = 91.043(9), V = 4751(1)Å3, Z = 4; R = 0.050 andRw = 0.058 for4497 reflections. 7·CH3OH:monoclinic, P21/n, a =18.812(2) Å, b = 16.156(2) Å, c =21.760(2) Å, =112.836(9), V = 6095(1) Å3,Z = 4; R = 0.055 andRw = 0.064 for 5843 reflections.8·CH3OH: monoclinic,P21/n, a =18.845(6) Å, b = 16.105(3) Å, c =21.776(3) Å, = 112.78(2), V =6091(2) Å3, Z = 4; R =0.055and Rw = 0.061 for 5189reflections.
-2-(PhO)2PO2}{1-(PhO)2PO2}(CH3OH)2(H2O)](7, 49% yield). TheZnCo center is bridged by the XDK through its two carboxylate groupsand by a diphenyl phosphate ligand. Theother diphenyl phosphate is terminally coordinated to the zinc atom ina monodentate fashion. The Zn···Cointeratomic distance is 3.846(1) Å. An analogousbis(phosphate) homodinuclear complex,[Zn2(XDK){-2-(PhO)2PO2}{1-(PhO)2PO2}(CH3OH)2(H2O)](8), was prepared by reacting[Zn2(XDK)(acac)2(CH3OH)2](6) withdiphenyl hydrogen phosphate in 64% yield. Compound 8,which is isomorphous with 7, has anasymmetricaldizinc core bridged by XDK and a phosphate ligand (Zn···Zn= 3.869(2) Å). The monodentate diphenylphosphateligand dissociates from the dimetallic center of 8 insolution, as revealed by molar conductivity and 1Hand31P{1H} NMR spectroscopic studies.The resulting free phosphate ligand exchanges with the bridgingone inmethanol-d4. The present results provide auseful synthetic route to carboxylate-bridgedheterodimetalliccompounds, which are potential models for the active centers innonredox metalloproteins. Crystal data are asfollows. 2: monoclinic,P21/c, a =17.725(7) Å, b = 12.354(4) Å, c =21.815(6) Å, = 90.45(3), V =4777(2)Å3, Z = 4; R = 0.049 andRw = 0.051 for 3884 reflections withI > 3(I). 3: monoclinic,P21/c, a =17.292(2)Å, b = 12.450(1) Å, c = 21.717(2)Å, = 91.464(7), V = 4673.9(7)Å3, Z = 4; R = 0.046 andRw = 0.051 for3876 reflections. 4: monoclinic,P21/c, a =17.630(1) Å, b = 12.374(2) Å, c =21.771(2) Å, = 90.306(8),V = 4749.4(7) Å3, Z = 4;R = 0.041 and Rw = 0.049 for 3248reflections. 5: monoclinic,P21/c, a =17.817(2)Å, b = 12.241(3) Å, c = 21.786(2)Å, = 91.043(9), V = 4751(1)Å3, Z = 4; R = 0.050 andRw = 0.058 for4497 reflections. 7·CH3OH:monoclinic, P21/n, a =18.812(2) Å, b = 16.156(2) Å, c =21.760(2) Å, =112.836(9), V = 6095(1) Å3,Z = 4; R = 0.055 andRw = 0.064 for 5843 reflections.8·CH3OH: monoclinic,P21/n, a =18.845(6) Å, b = 16.105(3) Å, c =21.776(3) Å, = 112.78(2), V =6091(2) Å3, Z = 4; R =0.055and Rw = 0.061 for 5189reflections.