1 / 48

演 講 者：鍾柏源 指導老師：于淑君 博士 Date ： 2009/01/20

17 e -. Synthesis and Characterization of the 17-Valence Electron Tris(2-pyridyl)Phosphine Oxide Ligated Chromium Nitrosyl Complex. 演 講 者：鍾柏源 指導老師：于淑君 博士 Date ： 2009/01/20. Outline. Introduction - Discovery of 17-e - compounds - Classification of 17-e - compounds

tanika
Download Presentation

演 講 者：鍾柏源 指導老師：于淑君 博士 Date ： 2009/01/20

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. 17 e- Synthesis and Characterization of the 17-Valence Electron Tris(2-pyridyl)Phosphine Oxide Ligated Chromium Nitrosyl Complex. 演 講 者：鍾柏源 指導老師：于淑君 博士 Date：2009/01/20

  2. Outline • Introduction - Discovery of 17-e- compounds - Classification of 17-e- compounds - NO releasing complexes • Experimental - [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 - Characterization of 16-e-, 17-e- and 18-e- complexes • Conclusions - Plausible Formation Pathwaysfor 17-e- [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

  3. Paramagnetic Organochromium Complexeswith 17 Valence Electrons 17 e- 18 e- Strametz, H.; Fischer, E. 0. J. Organomet. Chem.1967, 10, 323

  4. 17-Valence Electron Organochromium Complexes (1) Hexacoordinated Species [CrL6]+ dppm = Ph2PCH2PPh2, LEt = carbenoid ligand, dmpe = Me2P(CH2)2PMe2 Michael C. Baird, Chem. Rev. 1988.88. 1217-1227

  5. 17-Valence Electron Organochromium Complexes (2) Cyclopentadienyl Species CpCrL3 dppb = Ph2P(CH2)4PPh2, dpph = Ph2P(CH2)6PPh2 Michael C. Baird, Chem. Rev. 1988.88. 1217-1227

  6. 17-Valence Electron Organochromium Complexes (3) Nitrosyl Species [Cr(NO)L5-nXn](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 ∠Cr-N-O = 174.3° 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 170.3° (3) 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. Photo-Induced Nitric Oxide Releasing Prakash, R.J. Am. Chem. Soc.2005, 127, 13758-13759 Ford, P. C. J. Am. Chem. Soc. 2006, 128, 3831-3837

  10. Photo-Induced Nitric Oxide Releaing (continued) Mascharak, P. K. J. Am. Chem. Soc. 2006, 128, 7166-7167.

  11. Paramagnetic Organochromium Complexes 16 e- , Triplet S = 1 17 e- , Doublet S = 1/2 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 = Mo , W M = Cr , Mo , W 18 e- , Singlet S = 0 18 e- , Singlet S = 0

  12. 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”

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

  14. UV and IR of [OP(2-py)3M(CO)3] M = Cr，Mo，W Purple 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. 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”

  16. Crystal structure of [OP(2-py)3M(CO)2(NO)](BF4) 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”

  17. 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”

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

  19. UV and IR of [OP(2-py)3M(CO)2(NO)](BF4)M = Cr ，Mo ，W Yellow 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. 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”

  21. 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”

  22. 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”

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

  24. UV and IR of [OP(2-py)3M(CO)(NO)2](BF4)2M = Cr ，Mo ，W Green 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”

  25. [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 Yield = 75 %

  26. 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

  27. IR of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

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

  29. Near-IR of 17-e- [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

  30. Crystal structure of 17-e-[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)

  31. Exp. B3LYP/6-31G(d) 457 400 735 Theoretical Studiesof the UV Spectrum of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

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

  33. 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.

  34. 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

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

  36. EPR and SQUID data of Cr complexes 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”

  37. XPS Data of Cr Complexes

  38. Possible Mechanism for the Formation of Triplet [OP(2-Py)3Cr(CO)2(NO)](BF4)

  39. Possible Mechanism for the Formation of Triplet [OP(2-Py)3Cr(CO)(NO)2](BF4)2

  40. Study of the Formation Mechanism for 17-e-[OP(2-py)3Cr(MeCN)2(NO)](BF4)2 (I)

  41. Study of the Formation Mechanism for 17-e-[OP(2-py)3Cr(MeCN)2(NO)](BF4)2 (II)

  42. Study of the Formation Mechanism for 17-e-[OP(2-py)3Cr(MeCN)2(NO)](BF4)2 (III)

  43. Plausible Formation Pathways for 17-e- complex

  44. NO-Trapping Experiment GSNO λmax = 546 nm Grossiand L., D’Angelo S. J. Med. Chem. 2005,48, 2622-2626.

  45. NO-Trapping Experiment [OP(2-py)3Cr(CO)(NO)2](BF4)2 + GSH In MeCN [OP(2-py)3Cr(CO)(NO)2](BF4)2 + GSH In MeCN and H2O 546 nm 546 nm 735 nm 735 nm

  46. Conclusions • We have synthesized a rare 17-electronic chromium complexe [OP(2-py)3Cr(MeCN)2(NO)](BF4)2in high yield. • Mechanism of the formation of 17-electron complex was proposed by using UV and IR spectrometrey spectrometer. • A solvent-induced release of NO radical was demonstrated for these Cr complexes. • These paramagnetic chromium complexes might be potentially useful nitric oxide (NO) delivery agents.

More Related