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17 e -. Synthesis and Characterization of the 17-Valence Electron Tris(2-pyridyl)Phosphine Oxide Ligated Chromium Nitrosyl Complex. Speaker : Po-Yuan Chung Supervisor : Prof. Shuchun Joyce Yu Date : 2008/06/16. Outline. Introduction - Discovery of 17-e - compounds

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17 e-

Synthesis and Characterization of the 17-Valence Electron Tris(2-pyridyl)Phosphine Oxide Ligated Chromium Nitrosyl Complex.

Speaker:Po-Yuan Chung

Supervisor : Prof. Shuchun Joyce Yu

Date:2008/06/16


Outline
Outline

  • Introduction

    - Discovery of 17-e- compounds

    - Classification of 17-e- compounds

    - Application

  • Experimental section

    - [OP(2-py)3M(CO)3-n(NO)n](BF4)n M = Cr, Mo, W ; n = 0~2

    - [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

    - Analyze the compounds of 16, 17 and 18 electrons

  • Conclusions

    - Plausible formation pathways


Paramagnetic organochromium complexes with 17 valence electrons
Paramagnetic Organochromium Complexeswith 17 Valence Electrons

17 e-

18 e-

Strametz, H.; Fischer, E. O. J. Organomet. Chem.1967, 10, 323


17 valence electron organochromium complexes
17-Valence Electron Organochromium Complexes

(1) Hexacoordinated Species

[CrL6]+

Michael C. Baird, Chem. Rev. 1988.88. 1217-1227


17 valence electron organochromium complexes1
17-Valence Electron Organochromium Complexes

(2) Cyclopentadienyl Species

CpCrL3

MICHAEL C. BAIRD, Chem. Rev. 1988.88. 1217-1227


17 valence electron organochromium complexes2
17-Valence Electron Organochromium Complexes

(3) Nitrosyl Species

[Cr(NO)L(5-n)Xn](2-n)+,n = 0~1

Wigley, D. E.; Walton, R. A. Organometallics 1982, 1, 1322-1327


Paramagnetic organochromium complexes with 17 valence electrons1
Paramagnetic Organochromium Complexeswith 17 Valence Electrons

17 e-

Linear - NO

IR (KBr) νNO 1611 cm-1

IR (hexanes) νNO 1631 cm-1

Peter Legzdins, J. Am. Chem. SOC. 1991, 113, 7049-7050


Ligand with only donating character stabilizes 17 electron structure

17 e-

18 e-

18 e-

17 e-

Ligand with Only σ- Donating Character Stabilizes 17 Electron Structure

π-acceptor ligands such as CO stabilize the 18 e- configuration in the neutral complexe.

Linear - NO

IR (Nujol) νNO 1667 cm-1

IR (THF) νNO 1676 cm-1

IR (Nujol) νNO 1709 cm-1

IR (MeCN) νNO 1710 cm-1

IR (Nujol) νCN 2326 cm-1

IR (Nujol) νCN 2297 cm-1

σ-donor ligands such as NH3 & MeCN stabilize the 17 e- cationic compounds.

Peter Legzdins, J.Am. Chem. SOC. 1994, 116, 6021-6022


The first electron transfer chain catalyzed ligand substitution reaction
The First Electron Transfer Chain Catalyzed Ligand Substitution Reaction

Poli, R. J. Am. Chem. Soc. 1992, 114, 1302


Paramagnetic organochromium complexes

M = Cr , Mo , W Substitution Reaction

18 e- , Singlet S = 0

Paramagnetic Organochromium Complexes

M = Cr

16 e- , Triplet S = 1

M = Mo , W

18 e- , Singlet S = 0

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”

M = Cr

17 e- , Doublet S = 1/2

M = Mo , W

No reaction


M = Cr , Mo , W Substitution Reaction

18 e- , Singlet S = 0

Synthesis of [OP(2-py)3M(CO)3]

M = Cr ,Mo ,W

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


Crystal structure of op 2 py 3 m co 3
Crystal structure of [OP(2-py) Substitution Reaction3M(CO)3]

M = Mo

M = Cr

S. Joyce Yu, J. Organomet. Chem. 1999, 588, 260–267


UV and IR of [OP(2-py) Substitution Reaction3M(CO)3]

M = Cr,Mo,W

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


M = Cr , Mo , W Substitution Reaction

M = Cr 16 e- , Triplet S = 1

M = Mo , W 18 e- , Singlet S = 0

Synthesis of [OP(2-py)3M(CO)2(NO)](BF4)

M = Cr ,Mo ,W

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


Crystal structure of op 2 py 3 m co 2 no bf 4
Crystal structure of Substitution Reaction[OP(2-py)3M(CO)2(NO)](BF4)

M = Cr

M = W

M = Mo

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


SQUID Data of [OP(2-py) Substitution Reaction3Cr(CO)2(NO)](BF4)

μeff = g(S(S+1))1/2 ;

S=1,g = 1.9790代入

μeff =2.80(計算值)

μeff = (3k/Nβ2)1/2(χmT)1/2

= 2.828(χmT)1/2

實驗值μeff :2.87

=> Triplet S = 1

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


理論值 Substitution Reactionμeff :2.80

實驗值μeff :2.87

Robert H. Crabtree, The organometallic chemistry of the transition metals, Wiley


Uv and ir of op 2 py 3 m co 2 no bf 4 m cr mo w
UV and IR Substitution Reactionof [OP(2-py)3M(CO)2(NO)](BF4)M = Cr ,Mo ,W

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


Synthesis of op 2 py 3 m co no 2 bf 4 2 m cr mo w

M = Cr , Mo , W Substitution Reaction

M = Cr 16 e- , Triplet S = 1

M = Mo , W 18 e- , Singlet S = 0

Synthesis of [OP(2-py)3M(CO)(NO)2](BF4)2M = Cr ,Mo ,W

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


Crystal structure of op 2 py 3 m co no 2 bf 4 2
Crystal structure of Substitution Reaction[OP(2-py)3M(CO)(NO)2](BF4)2

M = Cr

M = Mo

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


SQUID Data of [OP(2-py) Substitution Reaction3Cr(CO)(NO)2](BF4)2

μeff = g(S(S+1))1/2 ;

S=1,g = 1.9560代入

μeff =2.77(計算值)

μeff = (3k/Nβ2)1/2(χmT)1/2

= 2.828(χmT)1/2

實驗值μeff :2.86

=> Triplet S = 1

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


理論值 Substitution Reactionμeff :2.77

實驗值μeff :2.86

Robert H. Crabtree, The organometallic chemistry of the transition metals, Wiley


Uv and ir of op 2 py 3 m co no 2 bf 4 2 m cr mo w
UV and IR of [OP(2-py) Substitution Reaction3M(CO)(NO)2](BF4)2M = Cr ,Mo ,W

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


[OP(2-py) Substitution Reaction3Cr(MeCN)2(NO)](BF4)2

*

[OP(2-py)3Mo(CO)(NO)2](BF4)2

CD3NO2

[OP(2-py)3W(CO)(NO)2](BF4)2

Synthesis of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

M = Cr

17 e- , Doublet S = 1/2

M = Mo , W

18 e- , Singlet S = 0

M = Cr , Mo , W


IR of [OP(2-py) Substitution Reaction3Cr(MeCN)2(NO)](BF4)2

1eq NO

νCNνCNνNO

Cr 2323 2295 1753

νCOνCOνNO

Cr 2047 1970 1718

Mo 2036 1953 1685

W 2017 1933 1670

2eq NO

νCNνCNνNO

Cr 2323 2295 1753

νCOνNOνNO

Cr 2029 1889 1742

Mo 2037 1826 1716

W 2148 1774 1687


UV of [OP(2-py) Substitution Reaction3Cr(MeCN)2(NO)](BF4)2

2eq NO

1eq NO


Crystal structure of op 2 py 3 cr mecn 2 no bf 4 2
Crystal structure of Substitution Reaction[OP(2-py)3Cr(MeCN)2(NO)](BF4)2

Bond angle (o)

C18-N6-Cr1:169.2(3)

C16-N4-Cr1:176.2(3)

O2-N5-Cr1:179.1(3)

Bond length (Å)

Cr1-N5:1.696(3)

Cr1-N4:2.044(3)

Cr1-N6:2.045(3)


Exp. Substitution Reaction

B3LYP/6-31G(d)

457

400

735

Theoretical studiesof

[OP(2-py)3Cr(MeCN)2(NO)](BF4)2


Theoretical studies of Substitution Reaction

[OP(2-py)3Cr(MeCN)2(NO)](BF4)2


Epr of op 2 py 3 cr mecn 2 no bf 4 2
EPR of [OP(2-py) Substitution Reaction3Cr(MeCN)2(NO)](BF4)2

gav = 1.9896

Solid

77 K

Wigley, D. E.; Walton, R. A. Organometallics1982, 1, 1322-1327.


SQUID Data of [OP(2-py) Substitution Reaction3Cr(MeCN)2(NO)](BF4)2

μeff = g(S(S+1))1/2 ;

S=0.5,g = 1.9896代入

μeff =1.72(計算值)

μeff = (3k/Nβ2)1/2(χmT)1/2

= 2.828(χmT)1/2

實驗值μeff :1.90

=> Doublet S = 1/2


理論值 Substitution Reactionμeff :1.72

實驗值μeff :1.90

Robert H. Crabtree, The organometallic chemistry of the transition metals, Wiley


Epr and squid data of cr complexes
EPR and SQUID data of Cr complexes Substitution Reaction

[OP(2-py)3Cr(MeCN)2(NO)](BF4)2 1.9896 1.72 / 2.09

林敬糧 碩士論文 2006 “亞硝醯基陽離子與C3v多吡啶磷和

氧化磷鉻羰錯合物的取代反應。有機鉻金屬路易士酸催化活性的探討”


MeCN Substitution Reaction

CV


CV of [OP(2-py) Substitution Reaction3Cr(CO)2(NO)](BF4)

Solvent: MeCN

Electrolyte:Tetrabutylammonium

perchlorate

-0.7187 V

-0.4986 V

1.4714 V

2.0250 V


Solvent Substitution Reaction: MeCN

Electrolyte:Tetrabutylammonium

perchlorate

0.1330 V

0.7085 V

0.2241 V

0.9985 V

CV of [OP(2-py)3Cr(CO)3


Solvent Substitution Reaction: MeCN

-0.6874 V

Electrolyte:Tetrabutylammonium

perchlorate

1.9430 V

CV of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2


16 e Substitution Reaction-

18 e-

17 e-

17 e-

17 e-

Peter Legzdins, Organometallics 1995, 14, 4721-4731

Peter Legzdins, J. Am. Chem. SOC. 1994,116, 6021-6022


Conclusions
Conclusions Substitution Reaction

  • We find a piece of special 17-electronic chromium compound, and characterize with IR, UV, CV, EPR, SQUID and X-ray.

  • We also try to put forward a rational mechanism to explain how to produce the 17-electron compound.


Plausible formation pathways for 17 e complex
Plausible Formation Pathways for 17-e Substitution Reaction- complex


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