advisor: zhu jun reporter: huang ying
DESCRIPTION
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 - PowerPoint PPT PresentationTRANSCRIPT
Advisor: Zhu JunReporter: Huang Ying
Si[Rh']
Si
[Rh]
R
R
Si[Os]
RSi[Os]
R
Ⅰ Conversion of osmasilabenzyne into silylene complexes
DFTPackage : Gaussian 03Method: B3LYPbasis sets : 6-31G * LanL2DZ (Os (f) = 0.886) (Si(d)= 0.262) (P (d) =0.340) (Cl(d) = 0.514))
Si[Os]
RSi[Os]
RG(
kcal/mol
Os
PH3
Cl
ClPH3
SiOs
H3P
Cl
ClH3P
Si
-21.2(-19.2)
Os
PH3
Cl
ClPH3
SiOs
H3PCl
ClH3P
Si-20.4(-30.5)
PH3+PH3
Guochen Jia, Coordination Chemistry Reviews, 2007, 251, 2167
Os
PH3
Cl
ClPH3
SiOs
PH3
Cl
ClPH3
Si
2
3
45
2 3
45
-21.2(-19.2)
G(kcal/mol
R=Me R= t-Bu R= n-pentyl
-16.9(-16.7)2
3
4
5
-25.1(-21.9)
-29.0(-26.0)
-40.3(-37.6)
-21.5(-21.3)
-23.4(-20.8)
-26.9(-24.7)
-31.0(-29.6)
-21.6(-20.6)
-22.6(-20.2)
-26.0(-23.8)
-29.4(-27.3)
R= OMe
-28.4(-27.5)
-17.6(-14.7)
-28.8(-27.2)
-23.8(-21.8)
R=NH2
-27.4 (-27.2)
-33.7(-31.1)
-9.2(-9.2)
-18.6(-16.6)
R=TMSR=NO2
-18.6(-18.2)
-18.2(-16.2)
-25.2(-23.1)
-15.5(-16.0)
-23.3(-20.9)
-24.7(-21.8)
-35.5(-33.2)
R= PMe3 R= PPh3
-20.7(-20.2)
-26.2(-24.0)
-18.3(-15.4)
-25.1(-23.1)
-20.8(-21.8)
-26.9(-24.3)
-19.8(-16.8)
-35.9(-34.1)
R=COOH
-23.7(-21.4)
-33.6(-31.8)
-25.0(-22.6)
R=CN
-23.8(-22.7)
-21.1(-18.6)
-29.6(-28.2)
-24.5(-21.9)
R=BH2
-16.9(-15.4)
-19.2(-16.1)
-18.2(-16.5)
-26.0(-23.6)
-23.9(-21.8)
-20.0(-19.7)
steric hindrance hydrogen bond
steric hindrance
substituents effect
Electronic effect + hydrogen bond
Os
PH3
Cl
ClPH3
Si
Os
PH3
Cl
ClPH3
Si-19.1(-18.2)
0.0(0.0)
Os
PH3
Cl
ClPH3
Si
Os
PH3
Cl
ClPH3
Si-19.9(-18.3)
0.0(0.0)
Os
PH3
Cl
ClPH3
Si
Os
PH3
Cl
ClPH3
Si-18.1(-14.4)
0.0(0.0)
PMe3
OMe Me3POMe
OMe
PMe3 OMe
PMe3
PMe3
PMe3
OMe PMe3OMe
PMe3
Os
PH3
Cl
Cl
PH3
Si
Os
PH3
Cl
Cl
PH3
Si-16.7(-16.3)
0.0(0.0)
Os
PH3
Cl
Cl
PH3
Si
Os
PH3
Cl
Cl
PH3
Si-18.9(-16.9)
0.0(0.0)
NH2
PMe3
Os
PH3
Cl
Cl
PH3
Si
Os
PH3
Cl
Cl
PH3
Si-18.4(-19.1)
0.0(0.0)
PMe3
Me3P
OMeOMe
NH2
NH2
PMe3NH2
NH2
NH2
Electronic effect
substituents effect
Os
PH3
Cl
ClPH3
Si
Os
PH3
Cl
ClPH3
Si-11.2(-10.7)
0.0(0.0)
Os
PH3
Cl
ClPH3
Si
Os
PH3
Cl
ClPH3
Si-12.2(-11.9)
0.0(0.0)
TMSOMe
TMS
OMe
TMS
PMe3
TMS
PMe3
Os
PMe3
Cl
ClPMe3
Si
Os
PMe3
Cl
ClPMe3
Si
-5.6(-6.9)
0.0(0.0)
TMS
NH2
TMS
NH2
steric hindrance + electronic effect
steric hindrance + hydrogen bond
Os
PMe3
Cl
ClPMe3
Si
Os
PMe3
Cl
ClPMe3
Si-7.3(-6.1)
0.0(0.0)
TMS
OMeTMS
OMe
substituents effect
Ligands effect
6.8(7.3)
12.5(15.1) (7.5)0.0(0.0)
0.0(0.0)
ligands=3PMe3
ligands=2CO.CH2CH2ligands=2PMe3.2OMe
Si
[Os]
..
Si
[Os]
Any
Si
Os
..CO
CO
Si
[Os]
Si
[Os]
OC
OC
Si
[Os]
Me3P
Me3P
MeO
MeO
Si
[Os]
..Si
[Os]Si
[Os]
Si
[Os]
..Si[Os]
Si
[Os]
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)
Os
PH3
Cl
ClPH3
SiC1
C2
C3C4
Si
Os
..PH3
PH3
H3PC1
C2
C3C4
ELF(electron localization function) 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, 2691Michael Haaf, Thomas A. Schmedake, Robert West, Acc. Chem. Res. 2000, 33, 704Yoshiyuki Mizuhata, Takahiro Sasamori, Norihiro Tokitoh, Chem. Rev. 2009, 109, 3479
The first stable silylene
And the later
2PMe3.P(OMe)3 -8.4(-8.0)3PMe3 -4.3(-1.5)
2PMe3.CNMe -2.6(-3.8)PMe3.bipyridine 2.2(3.4)
2PMe3.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.CH2CH2 -16.2(-14.2)
[Os] Si
Si
[Os]
..Five- coordinate
2NCH.2Cl -31.1(-29.8)
2P(OMe)3.2Cl -15.5(-13.0)
2CO.2Cl -31.7(-30.7)
2CH2CH2.2Cl -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)2CH2CH2.2H -24.1(-21.0)
Si[Os]
Os≡Si is a little longer than above
Cp.H 6.7(9.8)
ΔG(ΔE)
ΔG(ΔE)
-25.9(-27.3)2PMe3.2OMe
[Os] Si
Six- coordinate
Ligands
Jun Zhu, Guochen Jia, Zhenyang Lin, Organometallics, 2007, 26, 1986
Os
POMe3
H
HPOMe3
Si
Os
POMe3
H
HPOMe3
Si-3.4(-4.4)
0.0(0.0)
TMS
OMeTMS
OMe
OsCp
HSi
Os
H
Cp
Si
14.2(14.7)
0.0(0.0)
TMS
TMS
PMe3
PMe3
Si
Rh
CO
OC
OC
Si
Rh
OC
OC
OC
SiRh
CO
OC
OC
20.4(19.9) 30.8(31.4)0.0(0.0) -31.2(-22.0)
Si
Rh + CO
OC CO
Ⅱ. Isomerization from Silacyclopentadienyl Complexes to Rhodasilabenzenes
H.P. Wu, T. J. R. Weakley, M. M. Haley, Organometallics ,2002,21,4320
[Rh]
[Rh]
[Rh]
DFTPackage : Gaussian 03Method: m05basis sets : 6-31G * LanL2DZ (Rh (f) = 1.350) Si(d)= 0.262 P (d) =0.340 Cl(d) = 0.514)
ΔG(ΔE)/kcal.mol-
1 R=OMe R=SMe NH2 R=Me R=Ph R=t-Bu R=Br
2 21.7(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)
3 31.6(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)
4 26.0(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)
5 35.5(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)
6 22.6(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=COOH R=COOMe R=CN R=PMe3+ NO2 TMS
2 29.2(20.0) 30.4(20.6) 25.4(16.2) 23.6(12.5) 21.3(11.7) 38.2(27.4)
3 30.6(22.0) 31.3(22.0) 29.9(20.8) 30.4(21.2) 28.5(20.5) 34.6(24.3)
4 33.4(24.4) 33.5(24.2) 30.7(21.4) 31.8(22.8) 29.7(20.7) 35.6(25.8)
5 29.4(20.2) 29.8(20.6) 28.2(19.1) 27.6(18.3) 24.9(16.3) 34.8(24.9)
6 34.0(24.2) 33.9(24.2) 28.8(19.1) 35.3(24.9) 28.1(18.4) 41.8(31.5)
SiRh
Si
Rh
23
4
56
G(+ CO
31.2(22.0)
OC CO
CO
OC
OC
substituents effect
Si
RhOC CO
+CO
SiRh
CO
OC
OC
SiRh
CO
OC
OCSi
RhOC CO
+CO
SiRh
CO
OC
OCSi
RhOC CO
+CO
16.7(7.0)
0.0(0.0)
0.0(0.0)
0.0(0.0)
17.4(7.1)
5.0(-5.1)
SiRh
CO
OC
OC
25.2(15.8)
0.0(0.0)
SiRh
CO
OC
OC
17.0(7.0)
0.0(0.0)
Si
RhOC CO
+CO
Si
RhOC CO
+CO
Si
RhOC CO
+CO
SiRh
CO
OC
OC
0.0(0.0)
20.3(10.1)
NO2
OMe
MeO
O2N
MeO
OMe
OMe NO2
MeONO2
OMe
NO2
MeO NO2
OMe
MeO
NO2
MeO
MeO
NO2
OMe
MeO NO2
MeO
MeO NO2
OMeNO2
NO2
MeO
O2N
NO2
Si
RhOC CO
+CO
SiRh
CO
OC
OC
0.0(0.0)
16.4(6.2)
Si
RhOC CO
+CO
SiRh
CO
OC
OC
0.0(0.0)
20.0(8.3)
OMeNO2
OMe
MeO
MeO
MeO
O2NOMe
OMe
MeO
NO2
NO2
MeO
MeO
NO2
NO2
Si
RhOC CO
+CO
SiRh
CO
OC
OC 0.0(0.0)
13.7(3.2)OMe
OMe
MeO
MeO
MeO
OMe
NO2NO2
Si
RhOC CO
+CO
SiRh
CO
OC
OC
0.0(0.0)
21.4(10.1)OMe
OMe
MeO
MeO
MeO
OMe
NO2NO2
NO2 NO2
SiRh
CO
OC
OCSi
RhOC CO
+CO
OMe
OMe
MeO
MeO
MeO
OMe 0.0(0.0)
6.2(-4.6)
Si[Os]
Si[Os]
Si
[Os]
Si[Os]
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, 712Robert J. P. Corriu, Bhanu P. S. Chauhan, Gerard F. Lanneau, Organometallics,1995, 14, 164Hirroshi Ogino . The Chemical Record, 2002,2, 291
Some methods to synthesize M=Si
Si[Os]Si
[Os]How to synthesize
2. 1,2-elimination.
3. The Migration of α-H.
1. Through the light to get intermediates silylene
Si
Os
R R
X
Si
Os Si
Os
R R
Si
Os
R RSi
Os
R R
Si
Os
R R
Si
Os
R R
Paulus W. Wanandi, Paul B. Glaser, and T. Don Tilley, J. Am. Chem. Soc. 2000, 122, 972-973
The retrosynthetic analysis of osmasilabenzene
But
Si[Os]
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
[Os]Si
Me3Si
Me3Si
Et
BEt2
[Os] Si
Me3Si
Me3Si
Et
BEt2
[Os]
H B(C6F5)3Si
R
R
H
H
BEt3
100C-120CSi
H
H
R
R
Et
BEt2
Si
[Os]
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 work1. 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.
SiOs
PH3
PH3
-5.0Kcal/mol
H3P
Cl
-PH3
Si
OsH3P
H3PCl
0.0Kcal/mol
2. Try to explore some other transition metal.
Rh
PH3
Cl
ClPH3
SiSi
RhH3P
ClCl
4.9(-6.1)
0.0(0.0)
+ PH3
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