演 講 者：鍾柏源 指導老師：于淑君 博士 Date：2009/01/20 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 17 e-

Outline Introduction Experimental Conclusions - 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 Pathways for 17-e- [OP(2-py)3Cr(MeCN)2(NO)](BF4)2

Paramagnetic Organochromium Complexes with 17 Valence Electrons Strametz, H.; Fischer, E. 0. J. Organomet. Chem. 1967, 10, 323

17-Valence Electron Organochromium Complexes (1) Hexacoordinated Species [CrL6]+ complexes νCO, cm-1 gav [Cr(CO)6]+ 1.982 [trans-Cr(CO)4(PPh3)2]+ 1990 2.027 [cis-Cr(CO)4(dppm)] + 2084, 2033, 1969 2.009 [mer-Cr(CO)3(P(OMe)3)3]+ 2051, 1988, 1935 2.002 [mer-Cr(CO)3(PMe2Ph)3]+ 2010, 1940, 1904 2.019 [Cr(CO)3(dmpe)(LEt)] + 2010, 1930, 1890 dppm = Ph2PCH2PPh2, LEt = carbenoid ligand, dmpe = Me2P(CH2)2PMe2 Michael C. Baird, Chem. Rev. 1988. 88. 1217-1227

17-Valence Electron Organochromium Complexes (2) Cyclopentadienyl Species CpCrL3 complexes νCO, cm-1 (η5-C5H5)Cr(CO)2(PEt3) 1924, 1805 (η5-C5H5)Cr(CO)2(PBu3) 1921, 1803 (η5-C5H5)Cr(CO)2(PCy3) 1919, 1802 (η5-C5H5)Cr(CO)2(PPh3) 1920, 1800 (η5-C5H5)Cr(CO)2(PMe2Ph) 1925, 1807 (η5-C5H5)Cr(CO)2(PEt2Ph) 1923, 1807 [(η5-C5H5)Cr(CO)2]2(μ-dppb) 1915, 1806 [(η5-C5H5)Cr(CO)2]2(μ-dpph) 1915, 1795 dppb = Ph2P(CH2)4PPh2, dpph = Ph2P(CH2)6PPh2 Michael C. Baird, Chem. Rev. 1988. 88. 1217-1227

17-Valence Electron Organochromium Complexes (3) Nitrosyl Species [Cr(NO)L5-nXn](2-n)+ ，n = 0~1 complexes νNO, cm-1 νCN, cm-1 gav [Cr(NO)(CNCMe3)5](PF6)2 1805 2229 1.9936 [Cr(NO)(CNCHMe2)5](PF6)2 1770 2235 1.9931 [Cr(NO)(CNC6H11)5](PF6)2 1793 2240 1.9934 [Cr(NO)(CNCMe3)4Cl](PF6) 1742 2224 1.9927 [Cr(NO)(CNCHMe2)4Cl](PF6) 1746 2228 1.9925 [Cr(NO)(CNCMe3)4Br](PF6) 1744 2222 2.0146 [Cr(NO)(CNC6H11)4Br](PF6) 1734 2.0144 Wigley, D. E.; Walton, R. A. Organometallics 1982, 1, 1322-1327

Paramagnetic Organochromium Complexes with 17 Valence Electrons 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

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) 18 e- 17 e- 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

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

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

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

Synthesis of [OP(2-py)3M(CO)3] M = Cr ，Mo ，W M = Cr , 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”

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

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”

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

Crystal structure of [OP(2-py)3M(CO)2(NO)](BF4) M = Cr M = Mo M Cr Mo W ΔE(S-T) (kcal/mol) 26.5 39.9 56.5 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)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”

2 Triplet 2.83 理論值 μeff :2.80 實驗值 μeff :2.87 Spin Quantum Number, S Number of Unpaired Electrons Multiplicity Magnetic Moment Singlet 1/2 1 Doublet 1.73 2 Triplet 2.83 3/2 3 Quartet 3.87 4 Pentet 4.90 5/2 5 Sextet 5.92 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)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”

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

Crystal structure of [OP(2-py)3M(CO)(NO)2](BF4)2 M = Cr M = Mo M Cr Mo W ΔE(S-T) (kcal/mol) 11.4 26.4 32.8 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)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”

2 Triplet 2.83 理論值 μeff :2.77 實驗值 μeff :2.86 Spin Quantum Number, S Number of Unpaired Electrons Multiplicity Magnetic Moment Singlet 1/2 1 Doublet 1.73 2 Triplet 2.83 3/2 3 Quartet 3.87 4 Pentet 4.90 5/2 5 Sextet 5.92 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)3M(CO)(NO)2](BF4)2 M = 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”

Synthesis of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 M = Mo , W 18 e- , Singlet S = 0 M = Cr 17 e- , Doublet S = 1/2 M = Cr , Mo , W Yield = 75 % [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 [OP(2-py)3Mo(CO)(NO)2](BF4)2 [OP(2-py)3W(CO)(NO)2](BF4)2 * CD3NO2

IR of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 1eq NO νCN νCN νNO Cr 2323 2295 1753 νCO νCO νNO Cr 2047 1970 1718 Mo 2036 1953 1685 W 2017 1933 1670 2eq NO νCN νCN νNO Cr 2323 2295 1753 νCO νNO νNO Cr 2029 1889 1742 Mo 2037 1826 1716 W 2148 1774 1687

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

UV of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 complexes λmax / MeCN (nm) ε (L mol-1 cm-1) OP(2-py)3Cr(CO)3 530 7550 1eq 430 560 2eq 425 (667) 136 (24) 17e- 400 (735) 218 (53)

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

Crystal structure of 17-e- [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 cryst. Syst. Monoclinic space group P21/c　 a (Å) 11.4003(8) b (Å) 12.1182(8) c (Å) 24.2216(13) α (deg) 90.00 β (deg) 117.459(2) γ (deg) 90 V (Å3) 2969.3(3) Z 4 Bond length (Å) Cr1-N5：1.696(3) Cr1-N4：2.044(3) Cr1-N6：2.045(3) Bond angle (o) C18-N6-Cr1：169.2(3) C16-N4-Cr1：176.2(3) O2-N5-Cr1：179.1(3)

bond length (Å) X-ray B3LYP/6-31G* B3LYP/6-31+G* BLYP/6-31G* MPW1PW91/6-31G* Cr1 N5 1.696 1.723 1.729 1.689 1.725 N4 2.044 2.074 2.075 2.057 2.056 N6 2.045 N3 2.083 2.120 2.125 2.128 2.098 N2 2.124 N1 2.133 2.179 2.181 2.203 2.152 P1 O1 1.472 1.488 1.490 1.505 1.483 C16 1.131 1.158 1.157 1.171 1.155 C18 1.117 O2 1.156 1.176 1.188 1.172

bond angle (o) X-ray B3LYP/6-31G* B3LYP/6-31+G* BLYP/6-31G* MPW1PW91/6-31G* N5 Cr1 N4 92.2 91.4 91.9 91.1 N6 94.6 91.5 91.2 94.2 90.1 90.0 90.4 90.3 O1 P1 C1 114.0 115.0 114.8 115.2 115.1 C11 115.3 114.9 C6 114.2 O2 179.1 178.6 178.8 178.9 178.3

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

Theoretical studies of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 　cm-1) νNO νCN Exp. IR 1753 2295 2323 B3LYP/6-31G(d) 1870 2385 (asymm) 2388 (symm) scaled b 1798 2293 2296 B3LYP/6-31+G(d) 1850 2379 2381 MPW1PW91/6-31G(d) 1913 2419 2421

EPR of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 gav = 1.9896 Solid 77 K Wigley, D. E.; Walton, R. A. Organometallics 1982, 1, 1322-1327.

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

1/2 1 Doublet 1.73 理論值 μeff :1.72 實驗值 μeff :1.90 Spin Quantum Number, S Number of Unpaired Electrons Multiplicity Magnetic Moment Singlet 1/2 1 Doublet 1.73 2 Triplet 2.83 3/2 3 Quartet 3.87 4 Pentet 4.90 5/2 5 Sextet 5.92 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 [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”

XPS Data of Cr Complexes B.E. / eV A 572.5 B 574.9 C 576.3 D 575.4

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

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

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

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

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

Plausible Formation Pathways for 17-e- complex

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

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

Conclusions We have synthesized a rare 17-electronic chromium complexe [OP(2-py)3Cr(MeCN)2(NO)](BF4)2 in 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.