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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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slide1

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

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

slide11

M = Cr , Mo , W

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)3M(CO)3]

M = Mo

M = Cr

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

slide13

UV and IR 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”

slide14

M = Cr , Mo , W

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 [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”

slide16

SQUID Data of [OP(2-py)3Cr(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”

slide17

理論值μeff :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 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”

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

M = Cr , Mo , W

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 [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”

slide21

SQUID Data of [OP(2-py)3Cr(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”

slide22

理論值μeff :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)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”

slide24

[OP(2-py)3Cr(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

slide25

IR of [OP(2-py)3Cr(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

crystal structure of op 2 py 3 cr mecn 2 no bf 4 2
Crystal structure of [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)

slide30

Exp.

B3LYP/6-31G(d)

457

400

735

Theoretical studiesof

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

slide31

Theoretical studies of

[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)3Cr(MeCN)2(NO)](BF4)2

gav = 1.9896

Solid

77 K

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

slide33

SQUID Data of [OP(2-py)3Cr(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

slide34

理論值μeff :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

[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”

slide37

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

Solvent: MeCN

Electrolyte:Tetrabutylammonium

perchlorate

-0.7187 V

-0.4986 V

1.4714 V

2.0250 V

slide38

Solvent: MeCN

Electrolyte:Tetrabutylammonium

perchlorate

0.1330 V

0.7085 V

0.2241 V

0.9985 V

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

slide39

Solvent: MeCN

-0.6874 V

Electrolyte:Tetrabutylammonium

perchlorate

1.9430 V

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

slide40

16 e-

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
  • 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.
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