η6-苊烯三羰基铬配合物的合成、结构及光谱性质研究

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、1HNMR、13CNMR、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P21/c,Z=4,a=0.8719(7)nm,b=1.2436(10)nm,c=1.1504(9)nm,β=111.835(13)°,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).

Synthesis, Molecular Structure and Spectral Properties of η6- (Acenaphthylene) Chromium Tricarbonyl Complex

η6-(Acenaphthylene)chromium tricarbonyl complex was obtained as a racemic mixture of two enantiomers by treating the free ligand with (NH3)3Cr(CO)3 in refluxing tetrahydrofuran and characterized by IR, 1H NMR, 13C NMR,MS and elemental analysis. Purple-black crystals of C12 H8Cr(CO)3 form in the P21/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.