1. 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-

2. 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

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

4. 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

5. 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

6. 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,

7. Paramagnetic Organochromium Complexes with 17 Valence Electrons
Linear – NO ∠Cr-N-O = 174.3°
IR (KBr) νNO cm-1
IR (hexanes) νNO cm-1
Peter Legzdins, J. Am. Chem. SOC. 1991, 113,

8. 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 cm-1
IR (THF) νNO cm-1
IR (Nujol) νNO cm-1
IR (MeCN) νNO cm-1
IR (Nujol) νCN cm-1
IR (Nujol) νCN cm-1
σ-donor ligands such as NH3 & MeCN stabilize the 17 e- cationic compounds.
Peter Legzdins, J. Am. Chem. SOC. 1994, 116,

9. Photo-Induced Nitric Oxide Releasing
Prakash, R. J. Am. Chem. Soc. 2005, 127,
Ford, P. C. J. Am. Chem. Soc. 2006, 128,

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

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. 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”

13. Crystal structure of [OP(2-py)3M(CO)3]
M = Cr
M = Mo
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. Synthesis of [OP(2-py)3M(CO)2(NO)](BF4)
M = Cr ，Mo ，W
M = Cr , Mo , W
M = Cr e- , Triplet S = 1
M = Mo , W 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”

16. 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”

17. SQUID Data of [OP(2-py)3Cr(CO)2(NO)](BF4)
μeff = g(S(S+1))1/2 ;
S=1，g = 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. 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

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. Synthesis of [OP(2-py)3M(CO)(NO)2](BF4)2 M = Cr ，Mo ，W
M = Cr e- , Triplet S = 1
M = Mo , W 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”

21. 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”

22. SQUID Data of [OP(2-py)3Cr(CO)(NO)2](BF4)2
μeff = g(S(S+1))1/2 ;
S=1，g = 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. 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

24. 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”

25. 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

26. IR of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2
1eq NO
νCN νCN νNO Cr
νCO νCO νNO Cr Mo W
2eq NO
νCN νCN νNO Cr
νCO νNO νNO Cr Mo W

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

28. 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)

29. [OP(2-py)3Cr(MeCN)2(NO)](BF4)2
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
cryst. Syst.
Monoclinic
space group
P21/c　
a (Å)
(8)
b (Å)
(8)
c (Å)
(13)
α (deg)
90.00
β (deg)
(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)

31. 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

32. 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

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

34. 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

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

36. SQUID Data of [OP(2-py)3Cr(MeCN)2(NO)](BF4)2
μeff = g(S(S+1))1/2 ;
S=0.5，g = 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

37. 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

38. EPR and SQUID data of Cr complexes
[OP(2-py)3Cr(MeCN)2(NO)](BF4) /
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”

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

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

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

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

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

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

45. Plausible Formation Pathways for 17-e- complex

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

47. 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

48. 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.