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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

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

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  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.

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