Two Copper Complexes Based on Pyrazole-3-carboxylic Acid as Heterogeneous Catalysts for Highly Selective Oxidation of Alkylbenzenes
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摘要
Two new copper complexes based on pyrazole-3-carboxylic acid(H_2pca)ligand,Cu(Hpca)_2(H_2O)_2·2H_2O(1)and Cu_2(pca)_2(H_2O)_4(2)have been synthesized and fully characterized by single-crystal X-ray diffraction(SXRD),infrared spectroscopy(IR),thermal gravity analysis(TGA),powder X-ray diffraction(PXRD)and elemental analyses.Complex 1 is mononuclear while complex 2 shows a dinuclear structure.Complex 1 crystallizes in the monoclinic system,space group P2_1/c with Z=2,a=6.5591(5),b=21.696(2),c=4.9486(2)?,V=680.94(9)?~3,F(000)=366,D_c=1.745 g/cm~3,μ=1.650 mm~(-1),the final R=0.0340 and w R=0.0792.Complex 2crystallizes in the monoclinic system,space group P2_1/n with Z=2,a=5.1935(4),b=9.6052(7),c=12.7347(9)?,V=634.44(8)?~3,F(000)=420,D_c=2.195 g/cm~3,μ=3.404 mm~(-1),the final R=0.0305 and w R=0.0653.The three-dimensional frameworks of two complexes are formed by the O-H···O and N-H···O hydrogen bonding interactions.Notably,two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide(TBHP)as the oxidant and they exhibit excellent catalytic performance(Conv.up to 98.9%,Sele.up to 98.7%).
Two new copper complexes based on pyrazole-3-carboxylic acid(H_2pca)ligand,Cu(Hpca)_2(H_2O)_2·2H_2O(1)and Cu_2(pca)_2(H_2O)_4(2)have been synthesized and fully characterized by single-crystal X-ray diffraction(SXRD),infrared spectroscopy(IR),thermal gravity analysis(TGA),powder X-ray diffraction(PXRD)and elemental analyses.Complex 1 is mononuclear while complex 2 shows a dinuclear structure.Complex 1 crystallizes in the monoclinic system,space group P2_1/c with Z=2,a=6.5591(5),b=21.696(2),c=4.9486(2)?,V=680.94(9)?~3,F(000)=366,D_c=1.745 g/cm~3,μ=1.650 mm~(-1),the final R=0.0340 and w R=0.0792.Complex 2crystallizes in the monoclinic system,space group P2_1/n with Z=2,a=5.1935(4),b=9.6052(7),c=12.7347(9)?,V=634.44(8)?~3,F(000)=420,D_c=2.195 g/cm~3,μ=3.404 mm~(-1),the final R=0.0305 and w R=0.0653.The three-dimensional frameworks of two complexes are formed by the O-H···O and N-H···O hydrogen bonding interactions.Notably,two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide(TBHP)as the oxidant and they exhibit excellent catalytic performance(Conv.up to 98.9%,Sele.up to 98.7%).
Two new copper complexes based on pyrazole-3-carboxylic acid(H_2pca)ligand,Cu(Hpca)_2(H_2O)_2·2H_2O(1)and Cu_2(pca)_2(H_2O)_4(2)have been synthesized and fully characterized by single-crystal X-ray diffraction(SXRD),infrared spectroscopy(IR),thermal gravity analysis(TGA),powder X-ray diffraction(PXRD)and elemental analyses.Complex 1 is mononuclear while complex 2 shows a dinuclear structure.Complex 1 crystallizes in the monoclinic system,space group P2_1/c with Z=2,a=6.5591(5),b=21.696(2),c=4.9486(2)?,V=680.94(9)?~3,F(000)=366,D_c=1.745 g/cm~3,μ=1.650 mm~(-1),the final R=0.0340 and w R=0.0792.Complex 2crystallizes in the monoclinic system,space group P2_1/n with Z=2,a=5.1935(4),b=9.6052(7),c=12.7347(9)?,V=634.44(8)?~3,F(000)=420,D_c=2.195 g/cm~3,μ=3.404 mm~(-1),the final R=0.0305 and w R=0.0653.The three-dimensional frameworks of two complexes are formed by the O-H···O and N-H···O hydrogen bonding interactions.Notably,two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide(TBHP)as the oxidant and they exhibit excellent catalytic performance(Conv.up to 98.9%,Sele.up to 98.7%).
引文
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(2)(a)Yin,Y.;Tan,Z.;Hu,L.;Yu,S.;Liu,J.;Jiang,G.Isotope tracers to study the environmental fate and bioaccumulation of metal-containing engineered nanoparticles:techniques and applications.Chem.Rev.2017,117,4462-4487;(b)Han,C.B.;Wang,Y.L.;Liu,Q.Y.Crystal structure and magnetic properties of a dinuclear terbium compound Tb2(μ2-anthc)4(anthc)2(1,10-phen)2.Chin.J.Struct.Chem.2017,36,705-710.
(3)Paskevicius,M.;Jepsen,L.H.;Schouwink,P.;?erny,R;Ravnsb?k,D.B.;Filinchuk,Y.;Dornheim,M.;Besenbacher,F.;Jensen T.R.Metal borohydrides and derivatives-synthesis,structure and properties.Chem.Soc.Rev.2017,46,1565-1634.
(4)Zhao,Y.;Li,Z.;Sharma,U.K.;Sharma,N.;Song,G.;Eycken,E.V.V.Copper-catalyzed alkylarylation of activated alkenes using isocyanides as the alkyl source:an efficient radical access to 3,3-dialkylated oxindoles.Chem.Commun.2016,52,6395-6398
(5)?ili?,D.;Rakvin,B.;Mili?,D.;Paji?,D.;?ilovi?,I.Crystal structures and magnetic properties of a set of dihalo-bridged oxalamidato copper(II)dimers.Dalton Trans.2014,43,11877-11887.
(6)Teong,S.P.;Yu,D.;Sum,Y.N.;Zhang,Y.Copper catalysed alkynylation of tertiary amines with Ca C2 via sp3 C-H activation.Green Chem.2016,18,3499-3502.
(7)Tirsoaga,A.;Cojocaru,B.;Teodorescu,C.;Vasiliu,F.;Grecu,M.N.;Ghica,D.;Parvulescu,V.I.;Garcia,H.C-N cross-coupling on supported copper catalysts:the effect of the support,oxidation state,base and solvent.J.Catal.2016,341,205-220.
(8)Niu,M.;Li,Z.;Li,X.;Huang,X.Two chiral alkanolamine Schiff base Cu(II)complexes as potential anticancer agents:synthesis,structure,DNA/protein interactions,and cytotoxic activity.RSC Adv.2016,6,98171-98179.
(9)He,J.;Yin,Y.G.;Wu,T.;Li,D.;Huang,X.C.Design and solvothermal synthesis of luminescent copper(I)-pyrazolate coordination oligomer and polymer frameworks.Chem.Commun.2006,2845-2847.
(10)Fernandes,T.A.;Santos,C.I.M.;André,V.;K?ak,J.;Kirillova,M.V.;Kirillov,A.M.Copper(II)coordination polymers self-assembled from aminoalcohols and pyromellitic acid:highly active precatalysts for the mild water-promoted oxidation of alkanes.Inorg.Chem.2016,55,125-135.
(11)Artetxe,B.;Reinoso,S.;Felices,L.S.;Vitoria,P.;Pache,A.;Martín-Caballero,J.;Gutiérrez-Zorrilla,J.M.Functionalization of krebs-type polyoxometalates with N,O-chelating ligands:a systematic study.Inorg.Chem.2015,54,241-245.
(12)López-Viserasa,M.E.;Fernández,B.;Hilfiker,S.;González,C.S.;González,J.L.;Calahorro,A.J.;Colacio,E.;Rodríguez-Diéguez,A.In vivo potential antidiabetic activity of a novel zinc coordination compound based on 3-carboxy-pyrazole.J.Inorg.Biochem.2014,131,64-67.
(13)Liu,G.N.;Zhu,W.J.;Chu,Y.N.;Li,C.C.Three d10 metal coordination compounds based on pyrazole-3-carboxylic acid showing mixed-ligand characteristic:syntheses,crystal structures,and photoluminescent properties.Inorg.Chim.Acta 2015,425,28-35.
(14)Sheldrick,G.M.SHELXS-97,Program for X-ray Crystal Structure Solution.University of G?ttingen,Germany 1997.
(15)Brese,N.E.;O’Keeffe,M.Bond-valence parameters for solids.Acta Crystallogr.Sect.B 1991,47,192-197.
(16)Li,B.;Zhao,J.W.;Zheng,S.T.;Yang,G.Y.Hydrothermal synthesis and structure of di-copper(II)-complex substituted monovacant polyoxotungstate with a 1D chain structure.Inorg.Chem.Commun.2008,11,1288-1291.
(17)Chen,H.;Deng,Y.;Yu,Z.;Zhao,H.;Yao,Q.;Zou,X.;B?ckvall,J.E.;Sun,J.3D Open-framework vanadoborate as a highly effective heterogeneous pre-catalyst for the oxidation of alkylbenzenes.Chem.Mater.2013,25,5031-5036.
(18)Shi,D.;Ren,Y.;Jiang,H.;Lu,J.;Cheng,X.A new three-dimensional metal-organic framework constructed from 9,10-anthracene dibenzoate and Cd(II)as a highly active heterogeneous catalyst for oxidation of alkylbenzenes.Dalton Trans.2013,42,484-491.
(19)Yang,X.L.;Xie,M.H.;Zou,C.;He,Y.;Chen,B.;O’Keeffe,M.;Wu,C.D.Porous metalloporphyrinic frameworks constructed from metal5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin for highly efficient and selective catalyticoxidation of alkylbenzenes.J.Am.Chem.Soc.2012,134,10638-10645.
(20)He,Q.T.;Li,X.P.;Chen,L.F.;Zhang,L.;Wang,W.;Su,C.Y.Nanosized coordination cages incorporating multiple Cu(I)reactive sites:host-guest modulated catalytic activity.ACS Catal.2013,3,1-9.