| 芳基与烷基亚砜钯(II)配合物π反馈效应的DFT研究 |
| DFT Study on π Back-donation Effects of Aromatic and Alkyl Sulfoxide-palladium(II) Complexes |
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| 摘要: 应用DFT方法对二苯基亚砜(DPSO)和二己基亚砜(DHSO)的钯(II)配合物进行了理论计算。结果表明中心金属钯与亚砜之间存在d-π*反馈键，而且二苯基亚砜钯(II)配合物中的π反馈键比二己基亚砜钯(II)配合物强，即亚砜的取代基对其钯(II)配合物的π反馈键有显著的影响。以BHandH/6-31+G**(Pd，3-21G*)//BHandH/6-31G*(Pd，3-21G*)方法对相应的亚砜钯(II)配合物进行单点计算时，配合物trans-PdCl2(DPSO)2 的π反馈键轨道能为-10.695 eV，而trans-PdCl2(DHSO)2的π反馈键轨道能量为-10.320 eV。利用电子给体NH3或电子受体CO配位体置换亚砜钯(II)配合物里的一个亚砜配体后，Pd(II)-DHSO配合物的Pd-S配位键长的变化明显小于Pd(II)-DPSO配合物的Pd-S配位键长变化值，进一步说明在Pd-DPSO配合物中的π反馈效应强于相应的Pd-DHSO配合物。 |
| 关键词: 亚砜 钯(II)配合物 π反馈效应 DFT |
| 基金项目: |
| Abstract: Theoretical calculations on di-phenyl sulfoxide (DPSO) and di-n-hexyl sulfoxide (DHSO) Pd(II) complexes had been carried out by DFT method. d-π* back-donation bond could be found in these sulfoxide Pd(II) complexes, and π back-donation bond in DPSO-Pd (II) complex is stronger than that in DHSO-Pd(II) complex, indicating the substituent of sulfoxide ligand can influence Pd-sulfoxide d-π* back-donation interaction significantly. By BHandH/6-31+G**(Pd, 3-21G*)//BHandH/6-31G*(Pd, 3-21G*) method, the calculated d-π* back-binding orbital energy of trans-PdCl2 (DPSO)2 is -10.695 eV, which is slightly lower than that of trans-PdCl2 (DHSO)2 (-10.320 eV). The π back-donation effect on the Pd(II)-S bond lengths were further examined by calculations on model complexes [trans-PdCl2(CO)DHSO], [trans-PdCl2(NH3)DHSO], [trans-PdCl2(CO)DPSO] and [trans-PdCl2(NH3)DPSO] which contains σ-donor(NH3) or π-acceptor(CO) ligands. The change of Pd-S bond leng-ths in DHSO-Pd(II) complexes is obviously less than that in DPSO-Pd(II) complexes after the ligand substitution, suggesting DPSO-Pd(II) complex has a stronger π back-donation interaction than DHSO-Pd(II) complex. |
| Keywords: sulfoxide palladium(II) complex π back-donation effects DFT |
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| 摘要点击次数: 1590 |
| 全文下载次数: 1870 |
| 徐志广,古国榜,刘海洋.芳基与烷基亚砜钯(II)配合物π反馈效应的DFT研究[J].无机化学学报,2007,23(5):785-790. |
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