Advisor: Zhu Jun Reporter: Huang Ying. 1. Conversion of osmasilabenzyne into silylene complexes 2. Isomerization from Silacyclopentadienyl Complexes to.

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Presentation transcript:

Advisor: Zhu Jun Reporter: Huang Ying

1. Conversion of osmasilabenzyne into silylene complexes 2. Isomerization from Silacyclopentadienyl Complexes to Rhodasilabenzenes 3.literature research about the experiment 4.Future work

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

steric hindrance hydrogen bond steric hindrance substituents effect

Electronic effect + hydrogen bondElectronic effect substituents effect

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

Ligands effect 6.8(7.3) 12.5(15.1)(7.5)0.0(0.0) ligands=3PMe 3 ligands=2CO.CH 2 CH 2 ligands=2PMe 3.2OMe

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) ELF(electron localization function)

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 The first stable silylene And the later

2PMe 3.P(OMe) (-8.0) 3PMe (-1.5) 2PMe 3.CNMe -2.6(-3.8) PMe 3.bipyridine 2.2(3.4) 2PMe 3.NCH 2.3(2.9) ΔG(ΔE) Ligands Ligands effect CO.bipyridine 0.2(0.8) 3CO -11.3(-10.8) 2CO.CS -14.0(-13.4) 2CO.CH 2 CH (-14.2) Five- coordinate

2NCH.2Cl-31.1(-29.8) 2P(OMe) 3.2Cl-15.5(-13.0) 2CO.2Cl-31.7(-30.7) 2CH 2 CH 2.2Cl-27.2(-25.3) Ligands effect 2NCH.2H-25.7(-24.0) 2P(OMe) 3.2H-12.7(-9.7) 2CO.2H-21.2(-20.1) 2CH 2 CH 2.2H-24.1(-21.0) Os≡Si is a little longer than above Cp.H6.7(9.8) ΔG(ΔE) -25.9(-27.3)2PMe 3.2OMe Six- coordinate Ligands

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

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)= P (d) =0.340 Cl(d) = 0.514)

ΔG(ΔE)/kcal.mol -1 R=OMeR=SMeNH 2 R=MeR=PhR=t-BuR=Br 221.7(12.7)23.6(14.4)20.7(10.7)31.9(23.0)33.0(22.1)35.6(26.0)23.4(13.9) 331.6(23.0)31.7(21.2)32.5(22.9)31.7(22.8)32.2(23.0)35.4(25.6)29.4(19.7) 426.0(17.0)25.5(15.5)20.6(10.9)29.9(20.7)29.9(20.4)31.9(22.3)27.3(17.7) 535.5(25.9)30.7(21.0)34.5(24.6)32.6(23.9)32.6(22.8)34.6(25.6)28.6(19.2) 622.6(13.0)27.7(16.6)20.2(10.2)33.3(23.5)33.8(24.7)44.6(34.2)26.8(16.8) ΔG(ΔE)/kcal.mol -1 R=COOHR=COOMeR=CNR=PMe 3 + NO 2 TMS 229.2(20.0)30.4(20.6)25.4(16.2)23.6(12.5)21.3(11.7)38.2(27.4) 330.6(22.0)31.3(22.0)29.9(20.8)30.4(21.2)28.5(20.5)34.6(24.3) 433.4(24.4)33.5(24.2)30.7(21.4)31.8(22.8)29.7(20.7)35.6(25.8) 529.4(20.2)29.8(20.6)28.2(19.1)27.6(18.3)24.9(16.3)34.8(24.9) 634.0(24.2)33.9(24.2)28.8(19.1)35.3(24.9)28.1(18.4)41.8(31.5) substituents effect

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

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 Some methods to synthesize M=Si How to synthesize 2. 1,2-elimination. 3. The Migration of α-H. 1. Through the light to get intermediates silylene

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

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 Designed synthetic route of silylene complex

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

Summary 1.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. 2.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. 3. According to the synthetic route which we have designed, we can try to synthesize the silylene complexes and silacyclopentadienyl complexes.

Future work 1.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.

Thanks for your attention