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Advisor: Zhu Jun Reporter: Huang Ying

DFT study of rhodasilabenzene and osmasilabenzyne. Advisor: Zhu Jun Reporter: Huang Ying. Outline. 1. Conversion of osmasilabenzyne into silylene complexes 2. Isomerization from Silacyclopentadienyl Complexes to Rhodasilabenzenes literature research about the experiment

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Advisor: Zhu Jun Reporter: Huang Ying

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  1. DFT study of rhodasilabenzene and osmasilabenzyne Advisor: Zhu Jun Reporter: Huang Ying

  2. Outline 1. Conversion of osmasilabenzyne into silylene complexes 2. Isomerization from Silacyclopentadienyl Complexes to Rhodasilabenzenes • literature research about the experiment • Future work

  3. Ⅰ Conversion of osmasilabenzyne into silylene complexes DFT Package : Gaussian 03 Method: B3LYP basis sets : 6-31G * LanL2DZ (Os (f) = 0.886) (Si(d)= 0.262) (P (d) =0.340) (Cl(d) = 0.514)) Guochen Jia, Coordination Chemistry Reviews, 2007, 251, 2167

  4. substituents effect steric hindrance hydrogen bond steric hindrance 2 4

  5. substituents effect Electronic effect Electronic effect + hydrogen bond

  6. substituents effect steric hindrance + electronic effect steric hindrance + hydrogen bond

  7. Ligands effect ligands=3PMe3 0.0(0.0) 12.5(15.1) (7.5) ligands=2PMe3.2OMe ligands=2CO.CH2CH2 0.0(0.0) 6.8(7.3)

  8. ELF(electron localization function) ELF(electron localization function) NBO bond order(bond line) Os-Si=1.48(2.18) Os-C4=0.94(2.06) Si-C1=0.99(1.77) C3-C4=1.59(1.38) C2-C3=1.29(1.42) C1-C2=1.53(1.39) NBO bond order(bond line ) Os-Si=1.17(2.32) Os-C4=0.91(2.04) Si-C1=0.88(1.86) C3-C4=1.65(1.38) C2-C3=1.23(1.42) C1-C2=1.64(1.38)

  9. The first stable silylene And the later Michael Denk, J Robert Lennon, Randy Hayashi, Robert West, Alexander V. Belyakov, Hans P. Verne, Arne Haaland, Matthias Wagner, Nils Metzler, J. Am. Chem. Soc. 1994,116, 2691 Michael Haaf, Thomas A. Schmedake, Robert West, Acc. Chem. Res. 2000, 33, 704 Yoshiyuki Mizuhata, Takahiro Sasamori, Norihiro Tokitoh, Chem. Rev. 2009, 109, 3479

  10. Ligands effect Five- coordinate ΔG(ΔE) Ligands

  11. Ligands effect Six- coordinate Ligands ΔG(ΔE) 2PMe3.2OMe -25.9(-27.3) ΔG(ΔE) Os≡Si is a little longer than above

  12. Jun Zhu, Guochen Jia, Zhenyang Lin, Organometallics, 2007, 26, 1986

  13. Ⅱ. Isomerization from Silacyclopentadienyl Complexes to Rhodasilabenzenes H.P. Wu, T. J. R. Weakley, M. M. Haley, Organometallics ,2002,21,4320 DFT Package : Gaussian 03 Method: m05 basis sets : 6-31G * LanL2DZ (Rh (f) = 1.350) Si(d)= 0.262 P (d) =0.340 Cl(d) = 0.514)

  14. substituents effect

  15. Ⅲ literature research about the experiment Our experimental ultimate goal is to synthesize the M≡Si just be limited to early transition elements now Benjamin V. Mork and T. Don Tilley ,Angew. Chem. Int. Ed. 2003, 42,357

  16. Some methods to synthesize M=Si 1. Through the light to get intermediates silylene 2. 1,2-elimination. 3. The Migration of α-H. How to synthesize Rory .Waterman, Paul G. Hayes, T.Don Tilley, Acc. Chem. Res. 2007, 40, 712 Robert J. P. Corriu, Bhanu P. S. Chauhan, Gerard F. Lanneau, Organometallics,1995, 14, 164 Hirroshi Ogino . The Chemical Record, 2002,2, 291

  17. The retrosynthetic analysis of osmasilabenzene But Paulus W. Wanandi, Paul B. Glaser, and T. Don Tilley, J. Am. Chem. Soc. 2000, 122, 972-973

  18. Designed synthetic route of silylene complex Ezzat Khan, Stefan Bayer, Rhett Kempe, Bernd Wrackmeyer, Eur. J. Inorg. Chem. 2009, 4416 Rory .Waterman , Paul G. Hayes,T.Don Tilley, Acc. Chem. Res, 2007, 40, 712

  19. Designed synthetic route of Silacyclopentadienyl Complex William P. Freeman, T. Don Tilley, J. Am. Chem. SOC. 1994,116, 8428

  20. Summary • Theoretical calculations at the B3LYP level of density functional theory have been carried out to study the migratory insertion reactions from osmasilabenzynes complexes to silylene complexes , and Realize the isomerization from osmasilylene complex to osmasilabenzyne in thermodynamic. • Theoretical calculations at the m05 level of density functional theory have been used to explore the isomerization from silacyclopentadienyl complexes to rhodasilabenzenes , and found that the effect of substituents in the six-membered ring play important roles in determining the relative stabilities. • According to the synthetic route which we have designed, we can try to synthesize the silylene complexes and silacyclopentadienyl complexes.

  21. Future work • Continue to explore the migratory insertion reactions from osmasilabenzynes complexes to silylene complexes and the isomerization from silacyclopentadienyl complexes to rhodasilabenzenes, the main focus is their dynamical properties. 2. Try to explore some other transition metal. 3. Explore the isomerization from silacyclopentadienyl complexes to rhodanaphthalenes 4. Try to synthesize the silylene complexes and silacyclopentadienyl complexes. 5. Do some research of the migration of α-H 6. Try to get the stable triplet state of silylene in theory.

  22. Thanks for your attention

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