演講者 : 黃仁鴻 指導老師 : 于淑君 博士
DESCRIPTION
Synthesis, Characterization and Catalytic Application of Gold Nanoparticles-Supported Ni(II) Complex Catalyst. 演講者 : 黃仁鴻 指導老師 : 于淑君 博士. Types of Catalysts. Polystyrene-Supported Catalysts. Chem. Rev. 2002, 102, 3275-3300. Silica-Supported Catalysts. - PowerPoint PPT PresentationTRANSCRIPT
Synthesis, Characterization and CaSynthesis, Characterization and Catalytic Application of Gold Nanoparttalytic Application of Gold Nanoparticles-Supported Ni(II) Complex Cataicles-Supported Ni(II) Complex Cata
lystlyst
演講者 : 黃仁鴻
指導老師 : 于淑君 博士
2
Characteristics of catalysts Homogenous Heterogeneous Hybrid
Cat. structure Known Unknown Known
Catalyst modification Easy Difficult Easy
Activity High Low High
Selectivity High Low High
Conditions of catalysis Mild Harsh Mild
Poisoning of cat. High risk Low risk Low risk
Mechanical strength Low High High
Cat. stabilities Low High High
Separation & recycle of cat. Difficult Easy Easy
Industrialization Difficult Accessible Accessible
Types of CatalystsTypes of Catalysts
3Chem. Rev. 2002, 102, 3275-3300.
Polystyrene-Supported CatalystsPolystyrene-Supported Catalysts
4
Silica-Supported CatalystsSilica-Supported Catalysts
Chem. Rev. 2002, 102, 3495-3524.
5
Nanoparticles-Supported CatalystsNanoparticles-Supported Catalysts
Pfaltz, A. J. Am. Chem. Soc. 2005, 127, 8720-8731.
6
(EtO)3SiN
PPh2
PPh2
NC
O
H
O2
Oxidation
(EtO)3SiN
PPh2
PPh2
NC
O
HO
O
SiN
PPh2
PPh2
NC
O
H
OO
OEt
+RhL2
SiN
PPh2
PPh2
NC
O
H
OO
OEt
RhL2
O2 O
O
Metal Leaching
a. Oxidation
b. Metal Leaching
The Limitation of Phosphine LigandThe Limitation of Phosphine Ligand
Kinzel, E. J. Chem. Soc. Chem. Commun. 1986 1098.
7
Bipyridine LigandBipyridine Ligand
CMe2Ph
CMe2Ph
O N
N
N
O
N N N
H2PdCl4m
m
n
n
interior
surface
CMe2Ph
CMe2Ph
ON
N
N
O
N N
N
Pd2+
Pd2+
m
m
n
n
Buchmeiser, F. M. R. J. Am. Chem. Soc. 1998, 120, 2790.
Poly(N,N-bipyridyl-endo-norborn-2-ene-5-carbamide)10
8
MotivationMotivation
► Nickel is less expensive than other transition metal.
► To study the immobilization of molecular Ni(II) complexes on the surfaces of Au NPs by using the covalent techniques via a specially designed bipyridine ligand as spacer linkers.
► To investigate the reactivity of hybrid catalyst of this type and look into any possibility of reactivity changes due to the process of immobilization.
9
nanoparticleswith controllable solubility
soluble metal complex
functional groups
coordinationl ligands
spacer linker
Catalyst DesignCatalyst Design
catalyst
Au NPs have been known not only to possess solid surfaces resembling the (1 1 1) surface of bulk gold but also to behave like soluble molecules for their dissolvability, precipitability, and redissolvability.
Lin, Y.-Y; Tsai, S.-C.; Yu, S. J. J. Org. Chem. 2008, 73, 4920-4928.
10
Comparison of MComparison of M2+2+(d(d8 8 species)species)Square Planar vs. Tetrahedral ComplexesSquare Planar vs. Tetrahedral Complexes
Greenwood, Chemistry of the elements, Elsevier Science, 1997; p. 1347
• Ni => small Δt => tetrahedral & square planar Pd & Pt => large Δsp => square planar
• Ligands => large , weak-field => tetrahedral Ligands => small, strong-field => square planar
11R. G. Hayter, F. S. Humiec. Inorg. Chem. 1965, 12, 1701-1706.
Square Planar-Tetrahedral Isomerism of Square Planar-Tetrahedral Isomerism of Nickel Halide Complexes of Ni(PPhNickel Halide Complexes of Ni(PPh22R)R)22XX22
The tetrahedral structure is increasingly favored in the orders
P(C2H5)3 < P(C2H5)2C6H5 < PC2H5(C6H5)2 < P(C6H5)3
-Steric effect
SCN < Cl < Br < I -Due to the crystal field strength of the ligand decreases
12
Square Planar and Tetrahedral Structures Square Planar and Tetrahedral Structures of Ni[P(CHof Ni[P(CH22Ph)PhPh)Ph22]]22BrBr22
Kilbourn. B. T.; Powell. H. M. J. Chem. Soc. (A), 1970, 1688-1693.
Tetrahedral Square-Planar
13
NaN3 / DMF
rt / 6hr1
Br OH N3 OH
PBr3 / ether
rt / 3hr2
N3 Br
91 %
55 %
3
1. CS(NH2)2 / ethanol
2.reflux , 16 hr
3. NaOH / 5 min
4. HCl /20 min
HS N3
50 %
4
P(2-py)3
H2O / CH3CN
80 oC / 16 h
NHS
H
P
O
N
N
75 %
Synthesis of Spacer-LinkerSynthesis of Spacer-Linker
14
Synthesis of the RS-Au-L-NiBrSynthesis of the RS-Au-L-NiBr22 ( (77))
HAuCl4SS
SSSSSS
HS(CH2)11N(H) P(2-py)2
O
4
SS
Py2
SS
Py2
SS
Py2
SS
Py2
NiBr2(DME) / dry CHCl3SS
Py2NiBr2
SS
Py2NiBr2
SS
Br2NiPy2
SS
Br2NiPy2
4H2OCH3(CH2)7SH /CHCl3
NaBH4 / H2O
62 oC / 16 hr / CHCl3
CHCl3
rt / 12 hr
[CH3(CH2)7]4N+Br-
7
6
5
15
Synthesis of Molecular Ni(II)-CatalystSynthesis of Molecular Ni(II)-Catalyst
HO N3
P(2-py)3
H2O / CH3CN
80 oC / 16 h
NHO
H
P
O
NN
rt / 12h
NiBr2(DME)
dry CHCl3
NHO
H
P
O
NN
NiBr2
75 %
75 %
江柏誼碩士論文 2008
16
11H NMR Spectra of Au NPs H NMR Spectra of Au NPs 66 and and 77
*
*
#
#
d6-DMSO
RS-Au-L (6)
RS-Au-L-NiBr2 (7)
H2O
17
EPR Spectrum of RS-Au-L-NiBrEPR Spectrum of RS-Au-L-NiBr22 ((77))
0 2500 5000 7500-800
-600
-400
-200
0
200
400
600
inte
nsi
ty
[G]
RS-Au-L-NiBr2 (7)
RS-Au-L-NiBr2 (7) [Et4N]2[NiCl4]
Okada, K.; Matsushita, F.; Hayashi S. Clay Minerals 1997, 32, 299-305.
(powder, 77K, g = 2.55) g = 2.68
18
TEM Image of Octanethiol Protected TEM Image of Octanethiol Protected Au-SR Au-SR ((55))
Particle size distribution 4.4 ± 0.6 nm
SSSSSS
SS
5
19
TEM Image of RS-Au-L TEM Image of RS-Au-L ((66))
SS
Py2
SS
Py2
SS
Py2
SS
Py2
6
Particle size distribution 4.6 ± 0.6 nm
20
TEM Image of RS-Au-L-NiBrTEM Image of RS-Au-L-NiBr22 ((77))
SS
Py2NiBr2
SS
Py2NiBr2
SS
Br2NiPy2
SS
Br2NiPy2
7
Particle size distribution 4.9 ± 0.6 nm
21
300 400 500 600 700 8000
1
2
3
4
ab
s
nm
HS(CH2)
11N(H)P(O)(2-py)
2 (4, L)
Au-SR (5) RS-Au-L (6) RS-Au-L-NiBr
2 (7)
UV-vis Spectra of Ligand UV-vis Spectra of Ligand 44, and , and Au Nanoparticles Au Nanoparticles 55, , 66 and and 77
257 nm
517 nm
22
3000 2500 2000 1500 1000Wavenumber (cm-1)
HS(CH2)
11N(H)P(O)(2-py)
2 (4, L)
RS-Au-L (6) RS-Au-L-NiBr
2 (7)
IR Spectra of IR Spectra of 44, , 66 and and 77
1576 cm-1
1590 cm-1
23
3000 2500Wavenumber (cm-1)
HS(CH2)
11N(H)P(O)(2-py)
2 (4, L)
RS-Au-L (6) RS-Au-L-NiBr
2 (7)
IR Spectra of IR Spectra of 44, , 66 and and 7 7 in the in the ννSHSH Region Region
24
XPS Data of RS-Au-L-NiBrXPS Data of RS-Au-L-NiBr22 ((77))
92 90 88 86 84 82 80
500
1000
1500
2000
2500
3000
3500
4000
inte
nsi
ty (
Co
un
ts/s
ec)
Binding Energy (eV)
Au83.9
87.6
4f5/2
4f7/2
900 890 880 870 860 850
7800
8000
8200
8400
8600
8800
9000
9200
9400
9600
9800
inte
nsity
(C
ount
s/se
c)
Binding Energy
Ni
855.2872.9
2p1/22p3/2
25
Acetalization and Thioacetalization of CaAcetalization and Thioacetalization of Carbonyl Compoundsrbonyl Compounds
O
R R'
O
R H
HOOH
HO OH
HSSH
HS SH
Or else R"SH
Or else R"OH
O
O
O
O OR"
OR"
O
O
O
O OR"
OR"
S
S
S
S SR"
SR"
S
S
S
S SR"
SR"
Acetalization
Thioacetalization
26
Corey-Seebach ReactionCorey-Seebach Reaction
Seebach, D.; Jones, N. R.; Corey, E. J. J. Org. Chem. 1968, 33, 300-105.
n=2-6 n=2-6
Base
R
O
H
HS SH
Lewis Acid (cat.)S S
R H
BuLi
THF, -30oCS S
R Li
S S
R
normal reactivity:
R
O
H Nu:
masked acyl anion
E+
S S
R E
HgO
H2O/THF R
O
E
" "O
R
E+
27
Lewis Acid Catalyzed ThioacetalizationLewis Acid Catalyzed Thioacetalization
Conventional Lewis Acids BF3-Et2O 、 ZnCl2 、 AlCl3 、 SiCl4 、 LiOTf 、 InCl3
Nakata, T. et. al., Tetrahedron Lett. 1985, 26, 6461-6464.Evans, D. V. et. al., J. Am. Chem. Soc. 1977, 99, 5009-5017.Firouzabadi, H. et. al., Bull. Chem. Soc. Jpn. 2001, 74, 2401-2406.
Transition Metal Lewis AcidsTiCl4 、 WCl6 、 CoCl2 、 Sc(OTf)3 、 MoCl5 、 NiCl2Kumar, V. et. al., Tetrahedron Lett. 1983, 24, 1289-1292.Firouzabadi, H. et., al. Synlett 1998, 739-741.Goswami, S. et. al., Tetrahedron Lett. 2008, 49, 3092-3096.
Lanthanide Metal Lewis AcidsLu(OTf)3 、 Nd(OTf)3Kanta, D. S. J. Chem. Res. Synop. 2004,230-231.Kanta, D. S. Synth. Commun. 2004, 34, 230-231.
28
Nickel(II) Chloride Catalyzed Nickel(II) Chloride Catalyzed ThioacetalizationThioacetalization
O
H + HS SH S
S
2.5 hour
96 %
A. T. Khan et al., Tetrahedron Lett. 2003, 44, 919–922.
One use only
10 mole % NiCl2
29
Entry Time Yield(%)
1 2 min >99
2 40 min 96
3 10 min 98
4 2 hr 88
R
O
H
O
H
HO
O
H
OH
O
H
MeO
O
H
OMe
Entry Time Yield(%)
5 5 hr 92
6 15 hr 80
7 3 hr 92
8 1.5 hr 89
R
O
HO
H
O2N
O
H
NO2
O
H
NO2
R
O
H CH2Cl2 / MeOH, 25 oC R S
SHS
HS
RS-Au-L-NiBr2 (7) (10 mol%)
O
H
30
Entry Time Yield(%)
9 2 hr 89
10 60 min 98
11 4.5 hr 86
12 60 min 89
R
O
HEntry
Time Yield(%)
13 4.5 hr 70
14 60 min 94
R
O
H
H
O
O
H
H
O
O
H
O
H
H
O
R
O
H CH2Cl2 / MeOH, 25 oC R S
SHS
HS
RS-Au-L-NiBr2 (7) (10 mol%)
31
Entry Time Yield(%)
15 5 min >99
16 2.5 hr 97
17 30 min 93
18 4.5 hr 84
R
O
H
O
H
HO
O
H
OH
O
H
MeO
O
H
OMe
Entry Time Yield(%)
19 15 hr 88
20 18 hr 60
21 6.5 hr 83
22 2.5 hr 88
R
O
HO
H
O2N
O
H
NO2
O
H
NO2
R
O
H CH2Cl2 / MeOH, 25 oC R S
SHS SH
RS-Au-L-NiBr2 (7) (10 mol%)
O
H
32
Entry Time Yield(%)
23 2 hr 88
24 30 min 90
25 4.5 hr 75
26 30 min 88
R
O
HEntry
Time Yield(%)
27 5.5 hr 80
28 30 min 92
R
O
H
H
O
O
H
H
O
O
H
O
H
H
O
R
O
H CH2Cl2 / MeOH, 25 oC R S
SHS SH
RS-Au-L-NiBr2 (7) (10 mol%)
33
Entry Thiol Time Yield(%)
29 30 min 99
30 60 min 93
31 5 min 96
32 10 min 95
R
O
H
O
H
O
H
R
O
H
RS-Au-L-NiBr2 (7)
10 mol%
CH2Cl2 / MeOH, 25 oC
HS(CH2)nSH
n = 2, 3 RS
(CH2)nS
n = 2, 3aldehyde thiol
HS
HS
HS
HS
O
H
O
HHS SH
HS SH
34
Entry Time Yield (%)
Paper Reported cat. (NiCl2)
Time Yield (%)
8 1.5 hr 89 2.75 hr 96
1 2 min >99 8 min 96
3 10 min 98 45 min 90
5 5 hr 93 20 hr 82
R
O
H
O
H
O
H
HO
O
H
MeOO
H
O2N
R
O
H CH2Cl2 / MeOH, 25 oC R S
SHS
HS
Cat. (10 mole %)
35
Entry Time Yield (%)
Paper Reported cat. (NiCl2)
Time Yield (%)
22 2.5 hr 88 2.5 hr 94
15 5 min >99 30 min 93
17 30 min 93 1.15 hr 89
19 15 hr 88
R
O
H
O
H
O
H
HO
O
H
MeO
O
H
O2N
R
O
H CH2Cl2 / MeOH, 25 oC R S
SHS SH
Cat. (10 mole %)
36
Comparison of Catalytic Activity AmounComparison of Catalytic Activity Amoung Various Different Catalystsg Various Different Catalysts
+CH2Cl2 / MeOH, 25oC
Cat. (10 mole %)
O
H
HO HO
S
S
HS SH
Entry Cat. Time Yield (%)
A literature ( NiCl2 anhydrous) 30 min 93
B NONE 24 hr 96
C [HO(CH2)11N(H)P(O)(2-py)2]NiBr2 5 min >99
D RS-Au-L-NiBr2 (7) 5 min >99
37
Recycling Tests on Cat. Recycling Tests on Cat. 77 for T for Thioacetalization of Aldehydehioacetalization of Aldehyde
No metal leaching !!
+
RS-Au-L-NiBr2 (7)
CH2Cl2, 25 oC
20 mol%
O
H
HO HO
S
S
HS SH
Recycling NO.
Time(hr)
Yield (%)
1 1 94
2 1 96
3 1 97
4 1 96
5 1 96
6 1 97
7 1 96
8 1 96
9 1 93
10 1 93
11 1 92
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10 11 12Recycling NO.
Yie
ld (%
)
Filtrate no further reactivity
AA has no signal
38
Proposed Mechanism of ThiProposed Mechanism of Thioacetalizationoacetalization
O
HR
N
N Ni
Br
Br
O
R H
S SH
R
O
HS
SH
R
O
H
Ni
SSH
R S
SN
N NiBr
Br
R S
S
H
O
Ni
H
£_ +
HH
H2O
HO NH
P
O
NN
NiBr
Br
H
N
N Ni
Br
Br
39
Sythesis of Sythesis of αα-Aminonitrile-Aminonitrile
+ R3NH2 + HCN
NHR3
CNR2
O
R2R1
R1 + H2O
+ R3NH2 + TMSCN
CH3CN, 25 oC
NHR3
CNR2
O
R2R1
R1
NiCl25 mol%
De, S. K. J. Mol. Catal. A: Chem. 2005, 225, 169-171.
6 ~ 18 hr, 73% ~ 92%
40
The Various Modes of The Various Modes of αα-Aminonitrile -Aminonitrile ReactivityReactivity
Enders, D.; Shilvock, J. P. Chem. Soc. Rev. 2000, 29, 359-373.
41
Lewis Acid Catalyzed αLewis Acid Catalyzed α-Aminonitrile-Aminonitrile
Lewis acid catalysts Et3N 、 InCl3 、 Ga(OTf)3 、 BiCl3
Paraskar, A. S.; Sudalai, A. Tetrahedron Lett. 2006, 47, 5759-5762. Ranu, B. C.; Dey, S. S.; Hajra, A. Tetrahedron 2002, 58, 2529-2532. Surya Prakash, G. K.; Mathew, T. ; Panja, C.; Alconcel, S.; Vaghoo, H.; Do, C.; Olah, G. A. PNAS 2007, 104, 3703-3706. De, S. K. ; Gibbs, R. A. Tetrahedron Lett. 2004, 45, 7407-7408.
Transition metal Lewis acid catalysts RuCl3 、 NiCl2 、 Sc(OTf)3 、 Cu(OTf)2 De, S. K. Synth. Commun. 2005, 35, 653-656. De, S. K. J. Mol. Catal. A: Chem. 2005, 225, 169-171.
Lanthanide Lewis acid catalysts Pr(OTf)3 、 La(O-i-Pr) 、 Yb(OTf)3 De, S. K. Synth. Commun. 2005, 35, 961-966.
OthersKSF 、 I2 Yadav, J. S.; Subba Reddy, B. V.; Eeshwaraiah B.; Srinivas, M. Tetrahedron 2004, 60, 1767-1771. Royer, L.; De, S. K.; Gibbs, R. A. Tetrahedron Lett. 2005, 46, 4595-4597.
42
R-CHO + R1NH2 + TMSCN
RS-Au-L-NiBr2 5 mol%
CH3CN, 25 oC
NHR1
CNR
R
O
H
O
H
NH2
O
H
Cl
NH2
O
H
NH2
O
H
OMe
NH2
H
O NH2
>99105
88104
95153
97152
98151
Yield (%)Time(min)
R1NH2Entry
43
Proposed Mechanism of Proposed Mechanism of
αα-Aminonitrile-Aminonitrile
O
HR
N
N Ni
Br
Br
O
R H
NH
R
O
HNH R
O
H
Ni
NH
N
N NiBr
Br
O
Ni
H
£_ +
HH
S NH
P
O
NN
NiBr
Br
H
N
N Ni
Br
Br
Au
7
R1
R1 R1
R HN
HR1
Si CN
Si
OH
R CN
NHR1
44
ConclusionsConclusions
1. We have successfully synthesized an air- and water-stable and efficient interphase catalyst {Au NPs-S(CH2)11N(H)P(O)(2-py)2NiBr2}.
2. We use NMR 、 TEM 、 UV 、 IR 、 EPR and XPS for structural characterization of The Au NPs-Ni(II) catalyst.
3. The Au NPs-Ni(II) catalyst can be quantitatively recovered and effectively recycled for more than 11 times without any loss of reactivity.