Speaker ： Po-Yuan Chung Supervisor : Prof. Shuchun Joyce Yu Date ： 2008/06/16

1. 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

2. 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

3. Paramagnetic Organochromium Complexeswith 17 Valence Electrons 17 e- 18 e- Strametz, H.; Fischer, E. O. J. Organomet. Chem.1967, 10, 323

4. 17-Valence Electron Organochromium Complexes (1) Hexacoordinated Species [CrL6]+ Michael C. Baird, Chem. Rev. 1988.88. 1217-1227

5. 17-Valence Electron Organochromium Complexes (2) Cyclopentadienyl Species CpCrL3 MICHAEL C. BAIRD, Chem. Rev. 1988.88. 1217-1227

6. 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

7. 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

8. 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

9. The First Electron Transfer Chain Catalyzed Ligand Substitution Reaction Poli, R. J. Am. Chem. Soc. 1992, 114, 1302

10. 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

11. 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”

12. Crystal structure of [OP(2-py)3M(CO)3] M = Mo M = Cr S. Joyce Yu, J. Organomet. Chem. 1999, 588, 260–267

13. 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”

14. 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”

15. 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”

16. 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”

17. 理論值μeff :2.80 實驗值μeff :2.87 Robert H. Crabtree, The organometallic chemistry of the transition metals, Wiley

18. 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”

19. 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”

20. 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”

21. 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”

22. 理論值μeff :2.77 實驗值μeff :2.86 Robert H. Crabtree, The organometallic chemistry of the transition metals, Wiley

23. 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”

24. [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

25. 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

26. UV of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 2eq NO 1eq NO

27. 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)

30. Exp. B3LYP/6-31G(d) 457 400 735 Theoretical studiesof [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

31. Theoretical studies of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

32. 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.

33. 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

34. 理論值μeff :1.72 實驗值μeff :1.90 Robert H. Crabtree, The organometallic chemistry of the transition metals, Wiley

35. 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”

36. MeCN CV

37. 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

38. 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

39. Solvent： MeCN -0.6874 V Electrolyte：Tetrabutylammonium perchlorate 1.9430 V CV of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

40. 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

41. 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.

42. Plausible Formation Pathways for 17-e- complex