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用密度泛函理论PBE0法计算配合物[Fe(CO)x(Ph2Ppy)y(HgCl2)z](1:x=4,y=1,z=0;2:x=3,y=2,z=0;3:x=4,y=1,z=1;4:x=3,y=2,z=1;5:x=4,y=1,z=2;6:x=3,y=2,z=2)的几何构型,用PBE0-GIAO法计算配合物1～6的31P化学位移.计算结果表明,含2个Ph2Ppy的配合物5和6的Fe—Hg相互作用略大于含单个Ph2Ppy的配合物3和4.含2个HgCl2的配合物4和6存在Fe—Hgσ键,比含单个HgCl2的配合物3和5的Fe—Hg相互作用强,配合物3和5的Fe—Hg相互作用以Fe→Hg和Fe←Hg离域为主.配合物3中Fe的负电荷比5的小,故配合物5的Fe—Hg相互作用比配合物3的强且Fe→Hg离域比较显著,而配合物3的Fe←Hg离域更显著.Fe—Hg相互作用增大了双核配合物中P核周围的电子密度,其31P化学位移比相应的单核配合物小,且含2个HgCl2的双核配合物的31P化学位移更小.含单个Ph2Ppy的配合物的31P化学位移小于含2个Ph2Ppy的配合物.
The complex [Fe (CO) x (Ph2Ppy) y (HgCl2) z] (1: x = 4, y = 1, z = 0; 2: x = 3, y = 2 was calculated by density functional theory (PBE0) z = 0; 3: x = 4, y = 1, z = 1; 4: x = 3, y = 2, z = 1; 5: x = 4, y = 3, y = 2, z = 2), the chemical shifts of 31P of complexes 1 ~ 6 were calculated by PBE0-GIAO method.The calculated results show that Fe-Hg of complexes 5 and 6 containing two Ph2Ppy The effect is slightly larger than that of single Ph2Ppy-containing complexes 3 and 4. The complex Hgσ with two HgCl2 has Fe-Hgσ bonds, which is stronger than that of single HgCl2-complex 3 and 5. The complex 3 Fe-Hg and Fe-Hg interact with Fe → Hg and Fe ← Hg delocalization. The Fe in the complex 3 has a negative charge less than 5, so the Fe-Hg interaction of the complex 5 is stronger than that of the complex 3 And Fe → Hg delocalization is more significant, while the Fe ← Hg delocalization of complex 3 is more significant.Fe-Hg interaction increases the electron density around the P core in the binuclear complex, and the 31P chemical shift is higher than that of the corresponding mononuclear The complex has a small 31P chemical shift, and the binuclear complex containing two HgCl2s has a smaller 31P chemical shift than the one containing two Ph2Ppy.