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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

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

  • 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


substituents effect

steric hindrance

hydrogen bond

steric hindrance

2

4


substituents effect

Electronic effect

Electronic effect + hydrogen bond


substituents effect

steric hindrance + electronic effect

steric hindrance + hydrogen bond


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)


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)


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


Ligands effect

Five- coordinate

ΔG(ΔE)

Ligands


Ligands effect

Six- coordinate

Ligands

ΔG(ΔE)

2PMe3.2OMe

-25.9(-27.3)

ΔG(ΔE)

Os≡Si is a little longer than above



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)


substituents effect Rhodasilabenzenes


Ⅲ literature research about the experiment Rhodasilabenzenes

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


Some methods to synthesize M=Si Rhodasilabenzenes

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


The retrosynthetic analysis of osmasilabenzene Rhodasilabenzenes

But

Paulus W. Wanandi, Paul B. Glaser, and T. Don Tilley, J. Am. Chem. Soc. 2000, 122, 972-973


Designed synthetic route of silylene complex Rhodasilabenzenes

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 Silacyclopentadienyl Complex Rhodasilabenzenes

William P. Freeman, T. Don Tilley, J. Am. Chem. SOC. 1994,116, 8428


Summary Rhodasilabenzenes

  • 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.


Future work Rhodasilabenzenes

  • 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 Rhodasilabenzenes


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