摘要
利用二丁基氧化锡与N ,N 二甲基氨荒酸基乙酸以及N ,N 二乙基氨荒酸基乙酸反应 ,合成了二聚体有机锡化合物{[n Bu2 Sn(O2 CCH2 CS2 NMe2 ) ] 2 O}2 ( 1)和 {[n Bu2 Sn(O2 CCH2 CS2 NEt2 ) ] 2 O}2 ( 2 ) .通过元素分析 ,红外光谱及核磁共振谱对它们进行了表征 .并用X射线单晶衍射法测定了这两个化合物的晶体结构 ,结果表明 :1为单斜晶系 ,C2 /m空间群 ,晶胞参数为 :a =1 3 5 84( 5 )nm ,b =1 92 42 ( 7)nm ,c =1 464 0 ( 5 )nm ,β =10 2 5 0 5 ( 5 )° ,Z =2 ,V =3 73 6( 2 )nm3 ,μ =1 490g/cm3 ,F( 0 0 0 ) =170 4,R1=0 0 492 ,wR2 =0 115 9.2为三斜晶系 ,P1—空间群 ,晶胞参数为 :a =1 1960 ( 14 )nm ,b =1 3 612 ( 16)nm ,c =1 3 684( 16)nm ,α =90 969( 18)° ,β =10 5 2 41( 17)° ,γ =10 3 95 4( 16)° ,Z =1,V =2 0 78( 4 )nm3 ,μ =1 42 9g/cm3 ,F( 0 0 0 ) =916,R1=0 0 45 9,wR2 =0 0 95 7.它们都是以Sn2 O2 四元环为中心对称的二聚体结构 .但锡原子的配位方式不同 ,在 1中 ,内外环锡原子均为五配位的畸变三角双锥构型 ;而在 2中 ,内环锡原子为五配位的畸变三角双锥构型 ,而外环锡原子为六配位的加帽三角双锥构型 .
Two organotin compounds ｛[n-Bu 2Sn(O 2CCH 2CS 2NMe 2)] 2O｝ 2 (1) and ｛[n-Bu 2Sn(O 2~CCH 2~CS 2~NEt 2)] 2O｝ 2 (2) were synthesized by the reaction of n-dibutyltin oxide with N,N-dimethylthiocarbamoylthioacetic acid and N,N-diethylthiocarbamoylthioacetic acid in 1∶1 molar ratio, respectively. They were characterized by elemental analysis, IR, 1H and 119Sn NMR spectra and X-ray single crystal diffraction. The results showed that the compound 1 belongs to a monoclinic system with space group C2/m, and unit cell dimensions: a=1.3584(5) nm, b=1.9242(7) nm, c=1.4640(5) nm, β=102.505(5)°, Z=2, V=3.7362(2) nm 3, μ=1.490 g/cm 3, F(000)=1704, R 1=0.0492, wR 2=0.1159. The compound 2 belongs to a triclinic system with space group P1—, and unit cell dimensions: a=1.1960(14) nm, b=1.3612(16) nm, c=1.3684(16) nm, α=90.969(18)°, β=105.241(17)°, γ=103.954(16)°, Z=1, V=2.078(4) nm 3, μ=1.429 g/cm 3, F(000)=916, R 1=0.0459, wR 2=0.0957. The two compounds belong to centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn 2O 2 unit in which the bridging oxygen atoms are tri-coordinated. Each bridging oxygen atom also connects with an exo-cyclic tin atom. In the compound 1, the endo- and exo-cyclic tin atoms are all five-coordinated and have coordination geometry of distorted trigonal bipyramid. In the compound 2 the endo-cyclic tin atoms are five-coordinated and the exo-cyclic tin atoms are six-coordinated, and the two kinds of tin atoms have coordination geometry of distorted trigonal bipyramid and monocapped trigonal bipyramid respectively.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2004年第6期603-609,共7页
Acta Chimica Sinica
基金
国家自然科学基金 (No.2 0 2 71 0 2 5)
山东省自然科学基金 (No.L2 0 0 3B0 1 )资助项目
