摘要
合成了 {[( n-Bu) 2 Sn( 4-Fc-C6 H4COO) ]2 O}2 ( 1 )和 {[( n-Oct) 2 Sn( 4-Fc-C6 H4COO) ]2 O}2 ( 2 ) ( Fc=ferrocenyl)两种新的配合物 ,对其进行了元素分析 ,并用 IR,NMR( 1 H ,1 3C,1 1 9Sn)进行了谱学表征 .单晶 X射线衍射法测定表明 ,配合物 1的晶体属单斜晶系 ,P2 1 / c空间群 ,晶胞参数 a=1 .2 988( 1 ) nm,b=2 .4 655( 1 ) nm,c=3 .4 50 6( 1 ) nm,β=91 .556( 2 )°,V=1 1 .0 4 54( 1 ) nm3,Z=4 ,最终可靠因子 Rf=0 .0 71 ,Rw=0 .0 70 .分子 1为具有一个 Sn2 O2 四元中心内环的二聚结构 ,桥氧原子又各连接一个外环 Sn原子 ,呈三配位 .内环锡和外环锡采用略有不同的加帽三角双锥配位几何 . 4个羧酸酯基具有两种不同的配位方式 ,其中两个羧酸酯基通过其两个氧原子以桥式双齿分别跨接于一个内环锡和一个外环锡 ,而另外两个羧酸酯基则以单齿配位方式各与一个外环锡相连接 . Sn2 O2 中心内环与苯甲酸酯基、茂环等共轭体系之间相互未能共平面 .
In this paper, the novel compounds { [( n Bu) 2Sn(4 Fc C 6H 4COO)] 2O} 2(1) and { [( n Oct) 2Sn(4 Fc C 6H 4COO)] 2O} 2(2)(Fc=ferrocenyl) have been synthesized and characterized by elemental analysis, IR and NMR( 1H, 13 C and 119 Sn) spectroscopy. The crystal structure of compound 1 has been determined by single crystal X ray diffraction techniques. The crystal belongs to monoclinic with space group P2 1/c . The cell parameters are: a =1.298 8(1) nm, b =2.465 5(1) nm, c =3.450 6 (1) nm, β =91.556(2)°, V =11.045 4(1) nm 3, Z =4. The structure was refined to final R f=0.071, R w= 0.074 . Compound 1 is a dimer structure mode with a four member central endo cyclic Sn 2O 2 unit in which the bridged oxygen atoms are tri coordinated. Each bridged oxygen atom also connects an exo cyclic tin atom. Both endo and exo cyclic tin atoms are all five coordination and have coordination geometry of monocapped trigonal bipyramid with very similarly distorted mode. Four carboxylate ligands are divided into two types. Two of the carboxylate ligands are bidentate and bridging to each pair of exo and endo cyclic tin atoms by using both oxygen atoms. The others are monodentate and coordinate each exo cyclic tin atom. When considering further the longer distance interactions between the carboxyl oxygen in carboxylate ligand and endo cyclic tin atom (0.277 5—0.286 6 nm) and between the ester oxygen in carboxylate ligand and exo cyclic tin atom(0.298 0—0.300 6 nm), not only carboxylate ligand chelates to exo cyclic tin by anisobidentate mode but also their ester oxygen itself is tricoordinated and bridges to both endo and exo cyclic tin atoms. In compound 1, the coplanarity of two conjugate systems(benzoyloxy group and substituted Cp ring) is not good. And two conjugate systems can not be coplanar with the central endo cyclic Sn 2O 2 unit. Unlike the general com
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2000年第4期501-508,共8页
Chemical Journal of Chinese Universities
关键词
二烷基锡羧酸酯
二茂铁
谱学表征
晶体结构
Dialkyltin carboxylate
Ferrocene
Spectroscopic characterization
Crystal structure
