蝎型螯合过渡金属配合物的研究(Ⅰ)──氢三(3-对甲氧基苯基吡唑-1)硼酸铜(Ⅱ)配合物的合成、表征及晶体结构

Studies on Transition-metal Complexes Containing the Scorpionate Ligand(Ⅰ) Synthesis,Characterization and Crystal Structure of Copper(Ⅱ) Complexes with Hydrotris[3- (p- methoxyphenyl( pyrazol- 1 - yl) )]borate

合成了一种蝎合配体氢三 ( 3 -对甲氧基苯基吡唑 -1 )硼酸钾 KTp An.室温下 ,等物质的量的 KTp An与Cu( O2 CMe) 2 · H2 O在 THF溶液中反应得配合物 [Cu( O2 CMe) ( HB{pz An }3) ]( ) ;KTp An与等物质的量的无水 Cu Cl2 反应则得不同的产物 Cu Cl( pz An H) ( HB{pz An}3) ( ) .对标题化合物进行了元素分析、红外光谱、顺磁共振谱和电化学研究 .配合物 和 的苯溶液的 EPR谱研究表明中心金属铜的基态电子构型为拟轴对称的 {dx2 - y2 }1 . 的 X射线衍射晶体结构分析表明 ,铜离子的配位环境为畸变的四方锥结构 ,与其配位的有配体 Tp An上 3个吡唑氮原子、 3 -对甲氧基苯基吡唑氮原子和 1个氯离子 ,晶体属空间群 P2 1 /c.a=1 .1 64 3 ( 2 ) nm,b=2 .70 81 ( 5) nm,c=1 .4 494 ( 3 ) nm ,β=1 0 5.3 7( 3 )°,V=4 .4 0 66( 1 4 ) nm3,Z=4 ,R=0 .0 60 4 .分子中存在弱的分子内氢键 N— H… Cl,其中 Cl1… N1 =0 .3 0 0 9nm,∠Cl1… H1 B— N1 =1 2 0 .

A scorpionate ligand K[HB{pz An}3]( pz An=3- {p- methoxyphenyl}pyrazole) was prepared, which was reacted with one molar equivalent of Cu( O2 CMe) 2 · H2 O in THF at room temperature, yielding [Cu( O2 CMe) ( HB{pz An}3) ]( ) .But the reaction of K[HB{pz An}3]with anhydrous Cu Cl2 afforded Cu Cl( pz An H) ( HB{pz An}3) ( ) .The EPR spectra of and in benzene solution exhibit a pseudoaxial symmetrical {dx2 - y2 }1configuration at copper.Both and are characterized by IR, elementary analysis and CV.The crystal structure of compound has been determined.Crystals are monoclinic,space group P2 1/c with a=1 .1 643( 2 ) nm,b=2 .70 81 ( 5) nm,c=1 .4494( 3) nm,β= 1 0 5.37( 3)°,V=4.40 66( 1 4) nm3and Z=4,with final residuals R=0 .0 60 4 and Rw=0 .1 41 6.The complex shows a distorted square pyramidal copper center,and exhibits a weak intramolecular hydrogen bond,N _ H… Cl,with bond length of Cl… N 0 .30 0 9nm and bond angle of Cl… H _ N 1 2 0 .3°.