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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

slide2

Outline

1. Conversion of osmasilabenzyne into silylene complexes

2. Isomerization from Silacyclopentadienyl Complexes to Rhodasilabenzenes

  • literature research about the experiment
  • Future work
slide3

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

slide4

substituents effect

steric hindrance

hydrogen bond

steric hindrance

2

4

slide5

substituents effect

Electronic effect

Electronic effect + hydrogen bond

slide6

substituents effect

steric hindrance + electronic effect

steric hindrance + hydrogen bond

slide7

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)

slide8

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)

slide9

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

slide10

Ligands effect

Five- coordinate

ΔG(ΔE)

Ligands

slide11

Ligands effect

Six- coordinate

Ligands

ΔG(ΔE)

2PMe3.2OMe

-25.9(-27.3)

ΔG(ΔE)

Os≡Si is a little longer than above

slide13

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)

slide16

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

slide17

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

slide18

The retrosynthetic analysis of osmasilabenzene

But

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

slide19

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

slide20

Designed synthetic route of Silacyclopentadienyl Complex

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

slide21

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.
slide22

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.

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