摘要
用P(OC2 H5) 3 与母体簇Co6(μ6 P) (μ SCH2 CH2 CH2 S) (μ PSCH2 CH2 CH2 S) (CO) 12 进行取代反应得到一个二取代产物Co6(μ6 P) (μ SCH2 CH2 CH2 S) (μ PSCH2 CH2 CH2 S) (μ CO) (CO) 9[P(OC2 H5) 3 ]2 (Ⅰ ) ,同时还得到了两个一取代产物Co6(μ6 P) (μ SCH2 CH2 CH2 S) (μ PSCH2 CH2 CH2 S) (CO) 11[P(OC2 H5) 3 ](Ⅱa和Ⅱb ,Ⅱb是Ⅱa的一个同分异构体 ,其谱学数据与Ⅱa不同 ) .对合成的三个簇合物进行了元素分析、IR、1HNMR、3 1PNMR和MS谱学表征 ,对Ⅰ做了X射线单晶衍射测定 ,其晶体属于单斜晶系 ,P2 1/n空间群 ,晶胞参数 :a =1 1170 (2 )nm ,b =2 35 5 4(5 )nm ,c =1 7977(4 )nm ,β =99 5 0 (3)°,V =4 6 6 49(17)nm3 ,Z =4,Dc=1 76 3g/cm3 ,F(0 0 0 ) =2 488,μ =2 4 6 4cm-1.X射线晶体结构分析表明 ,取代位置发生在簇合物顶端的两个钴原子上 .晶体结构用直接法解出 ,经用全矩阵最小二乘法对原子参数进行修正 ,最后的偏离因子为R1=0 0 497,wR2 =0 1386 .
The hexanuclear cobalt carbonyl cluster compounds, disubstituted derivative Co-6(mu(6)-P)(mu-SCH2CH2CH2S)(mu-graphics PSCH2CH2CH2S)(mu-CO)(CO)(9)[P(OC2H5)(3)](2)(I ), and two monosubstituted derivatives Co-6(mu(6)-P) (mu-SCH2CH2CH2S) (mu-graphics PSCH2CH2CH2S) (CO)(11) [P(OC2H5)(3)] (II a and II b), were synthesized from the parent, Co-6(mu(6)-P)(mu-SCH2CH2CH2S)(mu-graphicsPSCH(2)CH(2)CH(2)S)(CO)(12), by substituting P(OC2H5)3 for two or one carbonyl groups, and the cluster derivatives were characterized by elemental analysis, IR, H-1 NMR, P-31 NMR and MS spectroscopies, respectively. Obviously, I b is an isomer of H a with different spectra data. The molecular structure of compound I was determined by using single crystal X-ray diffraction analysis, and the crystal is monoclinic, space group P2(1)/n, with alpha = 1. 1170(2) run, b = 2.3554(5) nm, c = 1.7997(4) nm, beta = 99.50(3)degrees, V = 4.6649(17) nm(3), Z = 4, D-c = 1.763 g/cm(3), F(000) = 2488, mu = 24.64 cm (-1). The structural analysis of compound I by X-ray diffraction identified the site of P(OC2H5)3 Substitution at the two apical Co atoms. The structure was solved by direct methods, and refined by full-matrix least-squares method. Finally, the departure factors are R-1 = 0. 0497 and wR(2) = 0.1386.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2002年第9期1644-1648,共5页
Acta Chimica Sinica
基金
国家自然科学基金 (No .2 0 176 0 48)资助项目
