摘要
采用苊烯配体与三胺基三羰基铬在四氢呋喃中回流反应 ,合成了 η6 -苊烯三羰基铬配合物 .通过元素分析、 IR、1 H NMR、1 3C NMR、 MS和 X射线单晶衍射对其结构进行了表征 ,比较了标题配合物与其自由配体的光物理行为 .晶体结构分析表明 ,标题配合物属单斜晶系 ,空间群 P2 1 /c,Z=4,a=0 .871 9( 7) nm,b=1 .2 43 6( 1 0 ) nm,c=1 .1 5 0 4( 9) nm,β=1 1 1 .83 5 ( 1 3 )°,Cr( CO) 3基团可与苊烯配体中的 2个苯环中的任意一个配位 ,形成 2个异构体 ( R,S) ,并以 1∶ 1的比例在其晶胞单元中反向面对面堆积 ,这种异构体共存于晶体中归属于 Cr( CO) 3基团在配体芳环之间的配位移动重排 ( IRHRs)
η6-(Acenaphthylene)chromium tricarbonyl complex was obtained as a racemic mixture of two enantiomers by treating the free ligand with (NH 3) 3Cr(CO) 3 in refluxing tetrahydrofuran and characterized by IR, 1H NMR, 13 C NMR,MS and elemental analysis. Purple-black crystals of C 12 H 8Cr(CO) 3 form in the P2 1/c space group with Z =4, a =0.871 9(7) nm, b =1.243 6(10) nm, c =1.150 4(9) nm , β =111.835(13)°. The full structure was determined by X-ray single crystal diffraction and the result indicated that chromium is η 6-coordinated to one six-membered ring of acenaphthylene. Face to face stack of coordinated aromatic rings by Cr(CO) 3 group on the outside is clearly observed between the two enantiomers possibly originated in the course of IRHRs (Inter-ring hatotropic rearrangements). Photophysical properties comparisons of the complex and the free ligand were also studied in advance.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2004年第8期1395-1399,M003,共6页
Chemical Journal of Chinese Universities
基金
国家自然科学基金 (批准号 :2 0 2 740 11)
上海市重点学科建设项目资助
关键词
苊烯
三羰基铬
合成
光谱性质
Acenaphthylene
Tricarbonyl chromium
Synthesis
Spectral property
