Synthesis And Characterization Of Organic Borate Ester Metallic Complexes

In this paper,2,6-diformyl-4-methylphenol(H3dfmp)and 1,2-cyclohexanedione dioxime(H2dpg)were used as ligands to form three functional metal ligand primitives containing Co,Mn and Fe metal ions.These primitives can coordinate with organic borate ligands by covalent bond to obtain six metal-organic acid complexes and five crystals of the complex.The structures and electrochemical properties were also characterized and analyzed.Using H3dfmp as raw material,two bimetallic center ligand primitives 1 and 2 were synthesized by dealing with cobalt nitrate and manganese chloride respectively.4-formylphenylboronic acid to form complex la(Et3NH[(C7H5O)B?{(H3L1)3Co?2}B?(C7H50)]).The primitive 2 reacts with[3-(nicotinamido)phenyl]boronic acid,4-Formylphenylboronic acid,[3-(benzoylamino)phenyl]boronic acid,and[3-(isonico tinamido)phenyl]boronic acid to form lb(Et3NH[(C12H9N2O)B?{(H3L1)3Mn?2}B?(C12H9N2O)]),lc(Et3NH[(C7H5O)B?{(H3L1)3Mn?2}B?(C7H50)]),1d(Et3NH[(C13 H10NO)B?{(H3L1)3Mn?2}B?(C13H10NO)])and le(Et3NH[(C12H9N2O)B?{(H3L1)3 Mn?2}B?(C12H9N2O)]),respectively.Using H2dpg as raw,metallic center liagnd primitive 3 was synthesized by dealing with ferric tetrafluoroborate.Then,primitive 3 reacts with 4-Formylphenylboronic acid to form complex 2a((C7H5O)B?{(H2L2)3 Fe?}B?(C7H5O)).The crystal of complex la was obtained through the evaporation of the CH30H:H20 =3:1 solution of complex la.The single crystal structure analysis showed that the crystal belongs to monoclinic system,C 2/c space group.The parameters of crystal:a = 25.870(15)A,b = 16.327(9)A,c = 23.666(14)A.a =90.00°,?= 99.89(10)°,? = 90.00°.Volume = 9677.9(10)A3,Z = 8,F(000)= 4320,R1= 0.0777,wR2 = 0.2263.Complex la is composed of the anionic on the ligand primitive of dinuclear Co?,protonated cation of H3dfmp and hydrone.The crystal of complex lb was obtained through the evaporation of the methanol solution of complex 1b.The single crystal structure analysis showed that the crystal belongs to monoclinic system,C 2/c space group.The parameters of crystal:a =24.842(15)A,b ? 15.193(9)A,c = 34.149(2)A.a = 90.00°,?= 104.63(10)°,?=90.00 °.Volume = 12470.2(13)A3,Z= 8,F(000)= 5408,R1=0.0716,wR2 = 0.1872.Complex 1b is composed of the anionic on the ligand primitive of dinuclear Mn?,protonated cation of H3dfmp and methanol molecules.The crystal of complex lc was obtained through the evaporation of the CH3OH:H2O =3:1 solution of complex lc.The single crystal structure analysis showed that the crystal belongs to monoclinic system,C 2/c space group.The parameters of crystal:a=25.964(12)A,b= 16.392(8)A,c = 23.858(12)A.a = 90 °,?=99.83(10)°,?=90.00 °.Volume = 10005.2(8)A3,Z = 8,F(000)= 4320,R1=0.0797,wR2 = 0.2565.Complex lc is composed of the anionic on the ligand primitive of dinuclear Mn?,protonated cation of H3dfmp and solvent molecules.The crystal of complex 1d was obtained through the evaporation of the methanol solution of complex 1d.The single crystal structure analysis showed that the crystal belongs to monoclinic system,C 2/c space group.The parameters of crystal:a=24.946(2)A,b= 15.139(13)A,c = 23.858(12)A.a = 90°,?=103.62(2)°,?=90.00 °.Volume = 12609.9(18)A3,Z= 8,F(000)= 5408,R1= 0.0782,wR2 = 0.1701.Complex 1d is composed of the anionic on the ligand primitive of dinuclear Mn?,protonated cation of H3dfinp and methanol molecules.The structure of complex le was confirmed through the infrared(IR),mass spectrometry(MS)and thermogravimetry(TGA).The crystal of complex 2a was obtained through the evaporation of the CH2Cl2:CH3(CH2)2CH3=3:1 solution of complex 2a.The single crystal structure analysis showed that the crystal belongs to monoclinic system,C 2/c space group.The parameters of crystal;a = 26.798(19)A,b=9.271(7)A,c = 15.662(7)A.a =90.00 °,?= 104.921(10)°,?= 90.00 °.Volume = 7032.3(9)A3,Z = 4,F(000)=3112,R1=0.0772,wR2=0.2210.The body skeleton of complex 2a is obtained from reaction of a Fe? ions,three H2dpg ions and two 4-formylphenylboronic acid at a ratio of 1:1:1.The electrochemical properties and redox properties of these organic metal complexes were analyzed and discussed using cyclic voltammetry(CV)and differential pulse method(DPV).Due to the presence of metal ions in these complexes,electron conduction of complex intramolecular exhibited multiple pairs of redox peaks,which were realized by electron coupling.In addition,the linear relationships between the maximum peak current and the square root of the scan rate were also studied.