吡唑-3-甲酸Cu(Ⅱ)/Mn(Ⅱ)配合物的合成、表征及常压下对二氧化碳催化转化（英文）
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摘要
合成和表征了2个吡唑-3-甲酸过渡金属配合物[Cu_2(pca)_2(H_2O)_6]·2H_2O(1),[Mn(Hpca)_2(phen)]·3H_2O(2)(H_2pca=吡唑-3-甲酸;phen=菲咯啉)。X射线单晶衍射分析结果表明,配合物1属于单斜晶系P21/n空间群,它是一个畸变八面体的双核铜配合物;配合物2是一个畸变八面体的单核锰配合物。配合物1和2分别通过分子间的O-H…O,N-H…O氢键形成了三维网状结构。配合物1在二氧化碳的环加成反应中显示出了良好的催化效率(转化率高达97.4%;选择性高达98.9%)。
Two transition metal complexes:Cu_2(pca)_2(H_2O)_6·2H_2O(1) and Mn(Hpca)_2(phen)·3H_2O(2)(H_2pca=pyrazole-3-carboxylic acid;phen =phenanthroline) have been prepared based on pyrazole-3-carboxylic acid and structurally characterized.The single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the monoclinic system P21/n space group and the binuclear copper center in 1 and mononuclear Mn (Ⅱ) center in 2 possess the distorted octahedral geometry.The three dimensional 3D framework of 1 and 2 are formed by the intermolecular O-H…O,N-H…O hydrogen bonding interactions.Importantly,complex 1 exhibits excellent heterogeneous catalytic performance(Conversion:up to 97.4%,Selectivity:up to 98.9%) in the catalytic conversion of CO_2 to cyclic carbonate.
Two transition metal complexes:Cu_2(pca)_2(H_2O)_6·2H_2O(1) and Mn(Hpca)_2(phen)·3H_2O(2)(H_2pca=pyrazole-3-carboxylic acid;phen =phenanthroline) have been prepared based on pyrazole-3-carboxylic acid and structurally characterized.The single crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the monoclinic system P21/n space group and the binuclear copper center in 1 and mononuclear Mn (Ⅱ) center in 2 possess the distorted octahedral geometry.The three dimensional 3D framework of 1 and 2 are formed by the intermolecular O-H…O,N-H…O hydrogen bonding interactions.Importantly,complex 1 exhibits excellent heterogeneous catalytic performance(Conversion:up to 97.4%,Selectivity:up to 98.9%) in the catalytic conversion of CO_2 to cyclic carbonate.
引文
[1]Han Y F,Jin G X.Acc.Chem.Res.,2014,47:3571-3579
[2]Lim D-W,Chyun S A,Suh M P.Angew.Chem.Int.Ed.,2014,53:7819-7822
[3]Wei T,Wang S,Lu X,et al.J.Am.Chem.Soc.,2016,138:207-214
[4](a)Zhang H,Lee J,Lammer A D,et al.J.Am.Chem.Soc.,2016,138:4573-4579(b)LI Zhi-Hua(李志华),LIU Hong(刘鸿),SONG Ling-Yong(宋凌勇),et al.Chinese J.Inorg.Chem.(无机化学学报),2017,33:237-242
[5]MAO Pan-Dong(毛盼东),ZHAO Xiao-Lei(赵晓雷),SHAO Zhi-Peng(邵志鹏),et al.Chinese J.Inorg.Chem.(无机化学学报),2017,33:890-896
[6]Lu Z,Abbina S,Sabin J R,et al.Inorg.Chem.,2013,52:1454-1465
[7]Liu G N,Zhu W J,Chu Y N,et al.Inorg.Chim.Acta,2015,425:28-35
[8]Hawes C S,Kruger P E.RSC Adv.,2014,4:15770-15775
[9]Sheldrick G M.SHELXS-97,Program for Crystal Structure Solution,University of Gottingen,Germany,1997.
[10]Sheldrick G M.SHELXL-97,Program for Crystal Structure Refinement,University of Gottingen,Germany,1997.
[11]WU Hao(吴浩),CHEN Ze-Hua(陈泽华),YU Ya-Ping(于亚平),et al.Chinese J.Inorg.Chem.(无机化学学报),2017,33:699-704
[12]Ma P,Zhang Y,Li J.J.Coord.Chem.,2014,67:2238-2248
[13]Yin F J,Zhao H,Xu X Y,et al.Chin.J.Struct.Chem.,2013,32:786-791
[14]Thuery P.Cryst Eng Comm,2013,15:6533-6545
[15]Leitner W.Angew.Chem.Int.Ed.,1995,34:2207-2221
[16]Benson E E,Kubiak C P,Sathrum A J,et al.Chem.Soc.Rev.,2009,38:89-99
[17]Appel A M,Bercaw J E,Bocarsly A B,et al.Chem.Rev.,2013,113:6621-6658
[18]Zou B,Hao L,Fan L Y,et al.J.Catal.,2015,329:119-129
[19]Wang W,Li C,Yan L,et al.ACS Catal.,2016,6:6091-6100
[20]Palgunadi J,Kwon O-S,Lee H,et al.Catal.Today,2004,98:511-514
[21]Tharun J,Kathalikkattil A C,Roshan R,et al.Catal.Commun.,2014,54:31-34
[2]Lim D-W,Chyun S A,Suh M P.Angew.Chem.Int.Ed.,2014,53:7819-7822
[3]Wei T,Wang S,Lu X,et al.J.Am.Chem.Soc.,2016,138:207-214
[4](a)Zhang H,Lee J,Lammer A D,et al.J.Am.Chem.Soc.,2016,138:4573-4579(b)LI Zhi-Hua(李志华),LIU Hong(刘鸿),SONG Ling-Yong(宋凌勇),et al.Chinese J.Inorg.Chem.(无机化学学报),2017,33:237-242
[5]MAO Pan-Dong(毛盼东),ZHAO Xiao-Lei(赵晓雷),SHAO Zhi-Peng(邵志鹏),et al.Chinese J.Inorg.Chem.(无机化学学报),2017,33:890-896
[6]Lu Z,Abbina S,Sabin J R,et al.Inorg.Chem.,2013,52:1454-1465
[7]Liu G N,Zhu W J,Chu Y N,et al.Inorg.Chim.Acta,2015,425:28-35
[8]Hawes C S,Kruger P E.RSC Adv.,2014,4:15770-15775
[9]Sheldrick G M.SHELXS-97,Program for Crystal Structure Solution,University of Gottingen,Germany,1997.
[10]Sheldrick G M.SHELXL-97,Program for Crystal Structure Refinement,University of Gottingen,Germany,1997.
[11]WU Hao(吴浩),CHEN Ze-Hua(陈泽华),YU Ya-Ping(于亚平),et al.Chinese J.Inorg.Chem.(无机化学学报),2017,33:699-704
[12]Ma P,Zhang Y,Li J.J.Coord.Chem.,2014,67:2238-2248
[13]Yin F J,Zhao H,Xu X Y,et al.Chin.J.Struct.Chem.,2013,32:786-791
[14]Thuery P.Cryst Eng Comm,2013,15:6533-6545
[15]Leitner W.Angew.Chem.Int.Ed.,1995,34:2207-2221
[16]Benson E E,Kubiak C P,Sathrum A J,et al.Chem.Soc.Rev.,2009,38:89-99
[17]Appel A M,Bercaw J E,Bocarsly A B,et al.Chem.Rev.,2013,113:6621-6658
[18]Zou B,Hao L,Fan L Y,et al.J.Catal.,2015,329:119-129
[19]Wang W,Li C,Yan L,et al.ACS Catal.,2016,6:6091-6100
[20]Palgunadi J,Kwon O-S,Lee H,et al.Catal.Today,2004,98:511-514
[21]Tharun J,Kathalikkattil A C,Roshan R,et al.Catal.Commun.,2014,54:31-34