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
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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]
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Conclusion
Results and Discussion
Introduction
Motivation
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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]
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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
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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
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Motivation
[M][M][M] [M]
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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.
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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
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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 .
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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]
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