speaker: ke an advisor: jun zhu 2013.05.03
DESCRIPTION
A Brief Insight into the Bridged- and Non-bridged Osmanaphthalene and the Osmaazulene Isomers. Speaker: Ke An Advisor: Jun Zhu 2013.05.03. Introduction. Motivation. Results and Discussion. Conclusion. Introduction. 1. The first metallapentalyne has been successfully synthesized. 1. - PowerPoint PPT PresentationTRANSCRIPT
Speaker: Ke AnAdvisor: Jun Zhu 2013.05.03
A Brief Insight into the Bridged- and Non-bridged Osmanaphthalene and the
Osmaazulene Isomers[M]
[M] [M] [M]
Conclusion
Results and Discussion
Introduction
Motivation
Introduction
1. C. Zhu; S. Li; M. Luo; X. Zhou; Y. Niu; M. Lin; J. Zhu; Z. Cao; X. Lu; T. Wen; Z. Xie; P. v. R. Schleyer; H. Xia. Nat. Chem. 2013. accepted.
1. The first metallapentalyne has been successfully synthesized.1
pentalyne戊搭炔 metallapentalyne
Antiaromatic Aromatic
[M]
Introduction
2. In 2003, the first non-bridged-iridanaphthalene was reported. 2,3
2. J. Chen, G. Jia, Coord. Chem. Rev. (2013), http://dx.doi.org/10.1016/j.ccr.2013.01.014.3. M. Paneque, C. M. Posadas, M. L. Poveda, N. Rendón, V. Salazar, E. O˜nate, K. Mereiter, J. Am. Chem. Soc. 2003, 125, 9898.
R = COOMe
N
N
O
N
N
NN
B
Me
Me
Me
Me
Me
Me
H
Ir
R
O
R R
R
Introduction
3. In 2007, the first non-bridged-osmanaphthalyne from zinc reduction of vinylcarbyne complex.
4. In 2009, selective synthesis of osmanaphthalene and osmanaphthalyne by C-H activation.
Z. Lin and G. Jia, Angew. Chem., Int. Ed. 2007, 46, 9065.
Os
PPh3
PPh3
PPh3
Cl
ClOs
Cl
Cl
PPh3
Os
Ph3PCl
PPh3
CC
OsCl
H
Cl
C
PPh3
PPh3
H
PPh3 PPh3BF4
BF4 BF4H
H84oC/ O2
acid84oC/ N2
ClCH2CH2Cl72%
PPh3 /
88%
Z. Cao and H. Xia, Angew. Chem., Int. Ed. 2009, 48, 5461.
OsPh3P
Ph3PCl
Zn
ZnCl2
Os
PPh3
ClPPh3
ClPPh3 HC C C OH
Cl
Cl
++
Cl Cl
Os
Cl
Ph3P
PPh3
Cl
Cl
Motivation
[M][M][M] [M]
Results and Discussion
The ISE value shows that naphthalene is more stable than azulene. All energies(kcal/mol) were calculated at B3LYP/6-31G* level, zero-point energy were applied.
E = -32.8
1. The comparison between azulene( 薁 ) and naphthalene.
Results and Discussion
1. The comparison between azulene and naphthalene.
NICS4(0) -17.4 -5.6 -8.5 -8.8
NICS(1) -17.8 -7.6 -10.4 -10.7
NICS(-1) -17.8 -7.6 -10.4 -10.7
BLA(Angstrom)
0.095 0.108 0.057 0.057
A B1.498
1.4051.403
1.390 1.396
1.396
C2v
A BD2h
1.415
1.374 1.420
1.431
Ring A
Ring A
Ring B Ring B
4. P. v. R. Schleyer; C. Maerker; A. Dransfeld; H. Jiao; N. J. R. v. E. Hommes. J. Am. Chem. Soc. 1996, 118, 6317.
Result 1: Azulene and naphthalene are both aromatic, which can be reflected by the negative NICS values and the BLA result.
NICS: Nucleus Independent Chemical Shift.BLA: Bond Length Alternation
Results and Discussion
2. The comparison between bridged-osmaazulene and osmanaphthalene. [Os] [Os]ISE= -18.8(1). [Os] = OsCl(PH3)2
NICS(0) 0.9 3.6 3.1 3.1
NICS(1) 1.8 1.7 -1.6 0.6
NICS(-1) -5.9 2.0 0.2 -4.7
BLA(C-C) 0.075 0.075 0.066 0.065
Dihedral Angel
-6.4 -42.3 14.1 11.9
Ring A
Ring B
Ring A
Ring B
[Os]
A B[Os]
A B
Result 2: The NICS values indicate the nonaromaticity of both molecules, which means the transition metal destroys the aromaticity of azulene and naphthalene .
Results and Discussion
[Os] [Os]ISE= -11.1(2). [Os] = OsCO(PH3)2
NICS(0) 29.0 24.3 19.4 18.5
NICS(1) 18.8 19.2 11.2 12.2
NICS(-1) 19.7 19.5 13.8 10.7
BLA(C-C) 0.036 0.081 0.045 0.070
Dihedral Angel
-1.6 -0.8 -8.4 -10.4
Ring A
Ring B
Ring A
Ring B
[Os]A B
[Os]
A B
2. The comparison between bridged-osmaazulene and osmanaphthalene.
Result 3: The NICS values indicate the antiaromaticity of both molecules, which means the transition metal reverses the aromaticity of azulene and naphthalene with the ligand influence.
Results and Discussion
3. The comparison between bridged-osmaazulene and osmanaphthalene in T1 state.
NICS(0) 3.2 0.7 -1.1 -1.2
NICS(1) 0.9 -0.9 -1.1 -1.7
NICS(-1) -0.9 1.5 -1.7 -1.2
BLA(C-C) 0.048 0.064 0.068 0.068
Dihedral Angel
1.1 2.2 -0.4 -0.6
Ring A
Ring B
Ring A
Ring B
[Os]A B
[Os]
A B
(1). [Os] = OsCl(PH3)2
[Os] [Os]ISE= -10.1
Result 4: In T1 state, bridged-osmanaphthalene is more stable. And the NICS values indicate the nonaromaticity of both compounds.
Results and Discussion
3. The comparison between bridged-osmaazulene and osmanaphthalene in T1 state.
(2). [Os] = OsCO(PH3)2
[Os] [Os]ISE= -7.4
NICS(0) -4.0 -5.0 -6.5 -6.5
NICS(1) -9.9 -6.8 -9.0 -9.2
NICS(-1) -9.2 -7.0 -9.2 -9.0
BLA(C-C) 0.028 0.020 0.020 0.020
Dihedral Angel
-0.3 -2.3 0 0.2
Ring A
Ring B
Ring A Ring B
[Os]
A B[Os]
A B
Result 5: The NICS values indicate the aromaticity of both molecules, which is just another demonstration of the antiaromaticity of the ground state.
Results and Discussion
4.The comparison between bridged-osmaazulene and non-bridged-osmaazulene.
(1). [Os] = OsCl(PH3)2 / OsCl(PH3)2H
E(kcal/mol)
E(kcal/mol)
0 -7.7
-12.9 -18.3
-5.3 -11.0
[Os]
1
2
56
7
[Os]
[Os]
[Os]
[Os]
[Os]
Result 6: Non-bridged-osmaazulene with chloride ligand is more stable than bridged-osmaazulene. The isomer of 6-CH group substituted by osmium fragment has the most negative values.
Results and Discussion
4.The comparison between bridged-osmaazulene and non-bridged-osmaazulene.
(1). [Os] = OsCl(PH3)2H
1 2 5 6 7
NICS(0) 4.0 0.1 -9.0 10.5 -4.0 -3.7 -8.3 -0.5 -4.6 -3.8
NICS(1) -5.2 -3.8 -18.3 6.2 -9.6 -7.1 -9.3 -3.6 -6.1 -5.9
NICS(-1)
-5.4 -3.7 -18.2 6.2 -10.0 -6.8 -8.9 -3.5 -6.4 -6.1
BLA(C-C)
0.106 0.109 0.105 0.123 0.114 0.123 0.089 0.096 0.125 0.132
Dihedral
-3.9 0.3 0.1 0.1 5.5 42.0 0.4 -32.2 1.7 5.9
[Os]
A B [Os] A B
[Os]
A B[Os]
A B [Os]A B
Explanation: The BLA result of the 6-subtituted isomer indicates result 6 again. The NICS values demonstrate the aromaticity of the non-bridged-osmaazulene isomers, except the seven-membered ring of the 2-substituted isomer.
Results and Discussion
4.The comparison between bridged-osmaazulene and non-bridged-osmaazulene.
(2). [Os] = OsCO(PH3)2 / OsCO(PH3)2H
E(kcal/mol)
E(kcal/mol)
0 6.1
-24.2 -9.4
-12.7 4.3
[Os]
[Os]
[Os]
[Os]
[Os]
[Os]
Result 7: Non-bridged-osmaazulene with CO ligand is more stable than bridged-osmaazulene except for 5- and 7-substituted isomers. The isomer of 1-CH group substituted by osmium fragment has the most negative values.
Results and Discussion
4.The comparison between bridged-osmaazulene and non-bridged-osmaazulene.
(2). [Os] = OsCO(PH3)2H
NICS(0) 1.1 -2.1 -3.3 11.1 -1.7 4.7 -4.2 -2.2 4.7 0.5
NICS(1) -6.5 -5.2 -11.0 6.2 -5.9 0.6 -7.5 -2.1 0.6 -3.6
NICS(-1)
-7.1 -5.2 -11.0 6.2 -6.5 1.0 -7.4 -0.9 1.0 -1.2
BLA(C-C)
0.080 0.088 0.121 0.122 0.156 0.164 0.086 0.095 0.146 0.148
Dihedral
0 0 0 0 -1.0 -16.8 -1.9 15.1 0.9 -5.7
[Os]
A B [Os] A B
[Os]
A B
[Os]
A B [Os]A B
Explanation: The BLA result of the 1-subtituted isomer and the larger BLAs of 5- and 7-substituted indicate result 7 again. The NICS values demonstrate the aromaticity of the 1- and 6-substituted isomers, except the seven-membered ring of the 2- and 5-substituted isomers and the five-membered ring of 7-substituted isomer.
Results and Discussion
4.The comparison between bridged-osmanaphthalene and non-bridged-osmanaphthalene.
(1). [Os] = OsCl(PH3)2 / OsCl(PH3)2H (2). [Os] = OsCO(PH3)2 / OsCO(PH3)2H
E(kcal/mol)
0
-19.3
-19.4
E(kcal/mol)
0
-27.2
-21.1
[Os]
1
2
[Os]
[Os]
[Os]
[Os]
[Os]
Result 8: Non-bridged-osmanaphthalene is more stable than bridged-osmaazulene. The isomer of 1-CH group substituted by osmium fragment with CO ligand has the most negative values.
Results and Discussion
4.The comparison between bridged-osmanaphthalene and non-bridged-osmanaphthalene.
NICS(0) -6.9 -2.7 -6.6 -0.6
NICS(1) -9.8 -4.3 -8.3 -3.1
NICS(-1) -9.6 -8.1 -8.1 -6.6
BLA(C-C)
0.051 0.083 0.052 0.094
Dihedral
1.0 31.1 2.1 11.3
[Os]
A B[Os]
A B
(1). OsCl(PH3)2H (2). OsCO(PH3)2H
NICS(0) -6.2 1.2 -4.2 0.5
NICS(1) -9.3 -3.6 -7.0 -4.8
NICS(-1) -9.2 -3.4 -7.1 -5.4
BLA(C-C) 0.050 0.063 0.076 0.069
Dihedral 0.1 1.1 0.2 -1.7
[Os]
A B[Os]
A B
Explanation: The BLA results indicate result 8 again. The NICS values demonstrate the aromaticity and stabilization of the non-bridged-osmanaphthalene isomers.
Conclusion
1. Azulene and naphthalene are both aromatic, and naphthalene is more stable than azulene.
2.Bridged-transition metal destroys the aromaticity of azulene and naphthalene. It’s nonaromatic with a chloride ligand and antiaromatic with CO ligand.
ISE = -32.8
[Os] [Os]
[Os] =OsCl(PH3)2Nonaromatic.
[Os]=OsCO(PH3)2Antiaromatic.
Conclusion
3. In T1 state, bridged-osmaazulene and osmanaphthalene are nonaromatic with a chloride ligand and aromatic with CO ligand.
[Os] [Os]
[Os] =OsCl(PH3)2Nonaromatic.
[Os]=OsCO(PH3)2Aromatic.
4. Non-bridged-osmaazulene and osmanaphthalene are more stable than bridged one. Due to the influence of the ligand, here are the most stable structures of osmaazulene and osmanaphthalene.
[Os]
[Os][Os]
[Os] =OsCl(PH3)2H
[Os] =OsCO(PH3)2H
[Os]