學生 : 王趙增 指導老師 : 于淑君 博士 2009 / 04 / 27 Department of Chemistry &...
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Molecular and Gold Nanoparticles Supported N-Heterocyclic Carbene Silver(I) Complexes – Synthesis, Characterization and Cataly
tic Applications
學 生 :王趙增指導老師 : 于淑君 博士
2009 / 04 / 27Department of Chemistry & Biochemistry
Chung Cheng University
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N-Heterocyclic CarbenesN-Heterocyclic Carbenes
NHCs are strongerσ-donors than the most electron rich phosphine- less likely to dissociate from the metal during the reaction
NHCs have come to replace phosphines in many organometallic and organic reactions
NHCs can be useful spectator ligands, tunable electronically and sterically
NHCs are most frequently prepared via deprotonation of the corresponding azolium salts
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N-Heterocyclic Carbenes as LigandsN-Heterocyclic Carbenes as Ligands- In the early 90's NHC were found to have bonding properties similar to trialklyphosphanes( -PR3 ) and alkylphosphinates( -OP(OR)R2 ).
- compatible with both high and low oxidation state metals
- examples:
- reaction employing NHC's as ligands:
Herrmann, W. Angew. Chem. Int. Ed. 2002, 41, 1290-1309.
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The Applications of Ag(I) NHCThe Applications of Ag(I) NHC
Silver(I)-Carbene Complexes as Carbene Transfer AgentsSilver(I)-Carbene Complexes as Carbene Transfer Agents
Addition of arenes to imines
Aza-Diels-Alder reaction
Asymmetric aldol reactionAsymmetric aldol reaction
Barbier-Grignard-type reactionBarbier-Grignard-type reaction
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The First Silver(I)-Carbene ComplexesThe First Silver(I)-Carbene Complexes
Arduengo.A.J,et.al. Organometallics 1993, 21, 3405-3409
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Silver(I)-Carbene Complexes as Carbene Silver(I)-Carbene Complexes as Carbene Transfer AgentsTransfer Agents
Wang, H. M. J.; Lin, I. J. B. Organometallics 1998, 17, 972-975
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MotivationMotivation
Using NHCs ligand to replace phosphine ligand in organUsing NHCs ligand to replace phosphine ligand in organomatallic catalysis.omatallic catalysis.--Immobilization of NHC- Ag(I) complexs onto Au NanoparticlesImmobilization of NHC- Ag(I) complexs onto Au Nanoparticles
Recyclable catalysts and their Applications in solvent-Recyclable catalysts and their Applications in solvent-free system.free system.
Developing a homogeneous catalyst for aldehyde alkyne Developing a homogeneous catalyst for aldehyde alkyne and amine coupling. and amine coupling.
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ExperimentalExperimentalPreparation of [Ag(hmim)Preparation of [Ag(hmim)22]PF]PF6 6 ComplexComplex
N N
N N
65 oC, 12h95 % yield
[Hmim]Br
Br N N
Br
[Hmim]PF6
PF6KPF6
DI 40oC/1h75 % yield
Ag2O, t-BuOK CH2Cl2 r.t / 4 h
75% Ag
NN
N N
PF6Ag
NN
N N
PF6
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11H NMR Spectra of [Hmim]HPFH NMR Spectra of [Hmim]HPF66, ,
[Ag(hmim)[Ag(hmim)22]PF]PF66
2H
H 2H
*DMSO
*H2O
*H2O
*DMSO
N N
PF6HH
H
2H
NN
Ag
H H
N N
PF6
HH
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1313C NMR Spectra of [Hmim]HPFC NMR Spectra of [Hmim]HPF66, ,
[Ag(hmim)[Ag(hmim)22]PF]PF66
c
N N
HC
PF6
C
Ag
C
C
NN
N N
PF6
*DMSO
*DMSO
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Change Temperature Change Temperature 11H NMR Spectra of H NMR Spectra of [Ag(hmim)[Ag(hmim)22]PF]PF66
Temp.:250C Temp.:100C
Ag
NN
N N
PF6Ag
NN
N N
PF6
H H
Ag
NN
N N
PF6
H
H
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ESI-MS Spectrum of [Ag(hmim)ESI-MS Spectrum of [Ag(hmim)22]PF]PF66
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(A) Addition of (a) HCl, (b) HBr, (c) HBF4, (d) HI,and (e) HPF6. (B) UV-vis absorption spectra corresponding to (a), (d), and (e) in photograph A.
Itoh, H.; Naka, K.; Chujo, Y. J. Am. Chem. Soc. 2004, 126, 3026-3027.
Ionic Liquids As Stabilizing Agents for NPsIonic Liquids As Stabilizing Agents for NPs
NN+
CH2 S
2
+
HAuCl4
6
NaBH4
S
Cl-
NN+
Cl-
Aun
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Synthetic StrategySynthetic Strategy
N N +Br
BrDMF / 80oC
12 hNN
Br
Br
1. CS(NH2)2 / ethanol
2. reflux , 16 hr
3. NaOH / 5 min
4. HCl /20 min
NNSH
Br
KPF6 NNSH
PF6
+DI/40oC
1 h
[Bhmim]Br
[Thmim]HBr [Thmim]HPF6
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Brust, M,; Walker, M.; Bethell, D,;Schiffrin, D, J.; Whyman, R.J. Chem. Soc. Chem. Commun. 1994, 801-802.
Particle size distribution = 2.1 ± 1.12 nm
Synthesis of Octanethiol Protected Au-SR NPs
HAuCl4 4H2OCH3(CH2)7SH /CHCl3
NaBH4 / H2OCHCl3
CH3(CH2)7]4N+Br-
ss
ss
s
ss
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Nano-Gold Surface-Immobilized ILsNano-Gold Surface-Immobilized ILs
NNSH S
SS
SSSSS
+
SN
S
S
S
Ligand- Exchange
THF / rt
N
N
N
N
N
N
N
S S
SS
X = PF6
7, X = PF6
X
X
XX
X
Au
Au
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SN
S
S
S
N
N
N
N
N
N
N
S S
SS
7, X = PF6
X
XX
X
Au
31P NMR 19F NMR
11H, H, 3131P, and P, and 1919F of F of Au NPs-Au NPs-SupportedSupported Ionic LiquidIonic Liquid
NNSH
PF6
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Particle size distribution =3.1 ± 1.3 nm
TEM and UV Spectra of Au NPs-TEM and UV Spectra of Au NPs-SupportedSupported Ionic LiquidIonic Liquid
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Au NPs-Supported Ag(I) Complexes via Au NPs-Supported Ag(I) Complexes via Thiolated NHC Carbene LigatiorThiolated NHC Carbene Ligatior
S N N
H H
Ag
S
NN
PF6
HH Au
SNN
Au
HH
Ag
S N N
PF6
H H
Au
PF6
S N NAu
H H
Ag
NN
HH
S
SN
S
S
S
N
N
N
N
N
N
N
S S
SS
7, X = PF6
X
XX
X
Au
Ag2O& t-BuOK
CH3CN r.t./ 4h
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Au
S N NAu
H H
H PF6
1 H 2 H
31P NMR 19F NMRPF6
S N NAu
H H
Ag
NN
HH
S
11H, H, 3131P, and P, and 1919F ofF of Au NPs-Supported Ag(I) ComAu NPs-Supported Ag(I) Complexes via plexes via
Thiolated NHC Carbene LigatiorThiolated NHC Carbene Ligatior
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TEM of Au NPs-Supported Ag(I) Complexes TEM of Au NPs-Supported Ag(I) Complexes via Thiolated NHC Carbene Ligatiorvia Thiolated NHC Carbene Ligatior
SN
S
S
S
N
N
N
N
N
N
N
S S
SS
7, X = PF6
X
XX
X
Au
S N N
H H
Ag
S
NN
PF6
HH Au
SNN
Au
HH
Ag
S N N
PF6
H H
Au
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S N NAu
H H
Ag
SNN
PF6
HH Au
S N NAu
H H
Ag
NN
PF6
HH
S
2H
2H
NN
Ag
H H
N N
PF6
HH
PF6
S N NAu
H H2H
NNSH
PF6
HH
2H
11H NMR Spectra of Ligand, Molcular and Au H NMR Spectra of Ligand, Molcular and Au Nanoparticles seriesNanoparticles series
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Au-SR
IL-SH
Au-IL
Au-IL-Ag
IR Spectra of Ligand & Au Nanoparticles seriesIR Spectra of Ligand & Au Nanoparticles series
imidazole H–C–C & H–C–N bending
1240 cm-1
1251cm-1
imidazole ν (ring stretching)
1560 cm-1
1571cm-1
-SH stretching
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A3-coupling reactions Have attracted much attention from organic chemists for the coupling products, propargylamines, which are major skeletons or synthetically versatile building blocks for the preparation of many nitrogen-containing biologically
active compounds
J. Org. Chem. 1995, 60, 1590-1594
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The First Silver-CatalyzedThree-Component Coupling of Aldehyde,
Alkyne, and Amine
Chao J. L. et. al. Org. Lett., Vol. 5, No. 23, 2003,4473-4475
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Proposed Mechanism Proposed Mechanism for the Three –Component Couplingfor the Three –Component Coupling
C-H activation
Silver (I)
Reduction
Silver(I)
Oxidation
Chao J. L. et. al. Org. Lett., Vol. 5, No. 23, 2003,4473-4475
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Solvents 1 Hr 2 Hr 4 Hr
[Hmim]Br 28.96% 45.73% 4 Hr 8 Hr
69.63% 82.37%
[Hmim]PF6 78.58% 87.27% 94.78%
Propionitrile 91.31% 96.08% 97.68%
Acetonitrile 73.23% 82.57% 96.35%
DMF 30 min 1 Hr 38% 4 Hr 6 Hr
36.08% 37.59% 38% 40%
1,4-dioxane 30 min 1 Hr 20% 4 Hr 6 Hr
11% 19% 23% 25%
H
O
+NH
+
H
1-ethynylbenzene
3 % AgPF6[hmim]2
1 mL Solvents
1 mmol 1.2 mmol 1.5 mmolpiperidine
benzaldehyde
Reaction conditions: Catalyst loading =1.5 mol%; carried out on a 1 mmol scale aldehyde/amine/alkyne = 1:1.2:1.5, 1000C, 1 mL of solvents.
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HR
O+ +
R
AgPF6[hmim]21.5 mol%
Propionitrile, reflux NH
N
Entry Time Yield(%) Paper Report cat. (AgI)
Time Yield(%)
1 30 min 95 % 2 hr 96 %
2 30 min 93 % 2 hr 79 %
3 30 min
8 hr
64.3 %
71 %
No test
4. n.d No test
5. 30 min 92 %92 % 2 hr 93 %
HR
O
HO
O
H
O
H
O
H
O
Reaction conditions: Catalyst loading =1.5 mol%; carried out on a 2 mmol scale aldehyde/amine/alkyne = 1:1.2:1.5, 1000C, 1 mL of Propionitrile.
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HR
O+ +
R
AgPF6[hmim]23 mol%
Propionitrile, reflux NH
N
Entry Time Yield(%) Paper Report cat. (AgI)
Time Yield(%)
1 30 min 95 % 2 hr 70%
2 2 hr2 hr
6 hr6 hr
70 %
90 %
2 hr 60%
3 n.d No test
HR
O
H
O
O
Br
O
Reaction conditions: Catalyst loading = 3 mol%; carried out on a 1mmol scale aldehyde/amine/alkyne = 1:1.2:1.5, 1000C, 1 mL of Propionitrile.
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Three-component coupling reactions catalyzed by a reusable PS-supported
NHC–Ag(I) under solvent-free reaction conditions
Li P. , Wang L. , Zhang Y. , Wang M. Tetrahedron Letters 49 (2008) 6650–6654
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Au-[hmim]2AgPF6: 9 mg
1,2,4,5-tetramethylbenzene: 5 mg
d6-DMSO
4 H 2 H
1,2,4,5-tetramethylbenzene
S N NAu
H H
Ag
NN
PF6
HH
S
0.25 : 0.13 = X : 0.03725X = 0. 07164 mmol – lignad0.07164×0.5 = 0.0358 mmol- metal center0.0358/9 = 0.004 mol/g
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NH
+neat ,2 h
+H H
O H2C N
20 mol % Au-[hmim]2AgPF6
1 2 3 4 5 66 77 88 99
93% 97% 96% 95% 93% 93% 91% 90% 91%
80%
90%
100%
0 2 4 6 8 10
Recycle No.
Con
vers
ion(
%)
Reaction conditions: Catalyst loading = 20mol%;para-formaldehyde(1.0mmol),piperidine(1.1mmol) phenylacetylene(1.1mmol) at room temperature for 24 h
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ConclusionsConclusions
1.We have developed a method to successfully immobilize (NHC)2AgPF6 onto surfaces of Au NPs was characterized by 1H-NMR,IR,TEM.
2.The air- and water- stable catalyst [Ag(hmim)2]PF6 was characterized by 1H- and 13C NMR, LC-MS, IR.
3. We have successfully demonstrated the catalytic activity of the Ag(I) complex for three component (aldehyde, alkyne, and amine) coupling reaction.
4. The Au NPs- Ag(I) hybrid catalysts can be easily recovered and reused many times without significant loss of reactivity.
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Immobilization of AgPFImmobilization of AgPF66(NHC) onto(NHC) onto
Surfaces of Au-NPsSurfaces of Au-NPs
H
2H
2H
S N N
PF6
Au
H H
H
S N NAu
H H
Ag
NN
PF6
HH
S
S N NAu
H H
Ag
SNN
PF6
HH Au
*H2O
*H2O
*DMSO
*DMSO
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IL-SH
Au-IL-Ag
Au-IL
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NH
+
1.1 mmol 1.1mmol
neat ,20 h+ piperidine 1-ethynylbenzene
H H
O
formaldehyde
1mmol
H2C N
2 mol % Au-[hmim]2AgPF6
11 22
95%95% 92%92%
Li P. , Wang L. , Zhang Y. , Wang M. Tetrahedron Letters 49 (2008) 6650–6654
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