Acta Phys. -Chim. Sin. ›› 2007, Vol. 23 ›› Issue (12): 1875-1880.doi: 10.1016/S1872-1508(07)60091-6

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Fe—Hg Interactions and 31P Chemical Shifts in [Fe(CO)3(PPh2R)2(HgCl2)] (R=pym, fur, py, thi)

LI Qin-Yu; XU Xuan   

  1. School of Chemistry and Environment, South China Normal University, Guangzhou 510006, P. R. China
  • Received:2007-05-14 Revised:2007-09-14 Published:2007-11-30
  • Contact: XU Xuan

Abstract: In order to study the effects of R group on Fe—Hg interactions and 31P chemical shifts, the structures of mononuclear complexes Fe(CO)3(PPh2R)2 (R=pym: 1, fur: 2, py: 3, thi: 4; pym=pyrimidine, fur=furyl, py=pyridine, thi=thiazole) and binuclear complexes [Fe(CO)3(PPh2R)2(HgCl2)] (R=pym: 5, fur: 6, py: 7, thi: 8) were studied by using the density functional theory (DFT) PBE0 method. The 31P chemical shifts were calculated by PBE0-GIAO method. Nature bond orbital (NBO) analyseswere also performed to explain the nature of the Fe—Hg interactions. The conclusions can be drawn as follows: (1) The complexes with nitrogen donor atoms are more stable than those with O or S atoms. The more N atom there are, the higher is the stabilitity of the complex. (2) The Fe—Hg interactions play a dominant role in the stabilities of the complexes. In 5 or 6, there is a σ-bond between Fe and Hg atoms, However, in 7 and 8, the Fe—Hg interations act as σP—Fe→nHg and σC—Fe→nHg delocalization. (3) Through Fe邛Hg interactions, there is charge transfer from R groups towards the P, Fe, and Hg atoms, which increases the electron density on P nucleus in binuclear complexes. As a result, compared with their mononuclear complexes, the 31P chemical shifts in binuclear complexes show some reduction.

Key words: DFT (PBE0), GIAO, Fe—Hg Interaction, 31P NMR, NBO


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