Selection of Two Optional Covalent Bonds by Electric Stimuli:

Dual Catalytic Switching of Redox-Active Copper Yu Kamamoto, Yuya Nitta, Kazuyuki Kubo, Tsutomu Mizuta and Shoko Kume*

Supporting Information

Materials and Equipments:

Phenylacetylene(EB), tetramethylethylenediamine(TMEDA), CuCl2, o-terphenyl were used as

purchased without further purification. Commercial tetra-n-butylammonium

hexafluorophosphate(nBu4NPF6) was recrystallized from methanol-water before use. CuCl2(tmeda)1,

ethynylferrocene(EF) 2 , benzylazide(AB) 3 , azidomethylferrocene 4 , 4-nitrophenylazide 5 ,

4-(N,N-dimethylamino)phenylazide(AN) 6 , 4-(triisopropylsilyl)ethynylbenzenediazonium

tetrafluoroborate (TIPS-Eth-N2•BF4)7 were prepared according to literature methods. All organic

solvents were distilled with appropriate drying reagents (CaH2, Mg or Na) and stored under N2.

A terminal alkyne modified glassy carbon electrode (Es) was prepared by cathodic grafting of

TIPS-Eth-N2•BF4 followed by a deprotection with nBu4NF, according to the literature procedure7. A

3 mm glassy carbon rod (Tokai Carbon) was embedded in a glass tube, and the cross section was

polished with an aluminum powder (50 nm) and used as a base electrode.

A stock solution of catalyst containing Cu(tmeda)Cl2 (0.12 molL-1) and TMEDA (0.11 molL-1)

were prepared and used in the surface electromodification experiment.

Electrochemical measurements were operated with ALS 600D electroanalyzer. A simultaneous

potential application to two electrodes was operated with ALS 600D electroanalyzer and HOKUTO

HAB-101 potentiostat. An Ag/Ag+ reference electrode ( E1/2 = 0.089 V for ferrocene/ferrocenium in

0.1 M nBu4NPF6 in MeCN) and a Pt wire as a counter electrode were immersed in an unseparated

electrochemical cell with the working electrode. The amounts of immobilized species were

quantified by an area calculation of a cyclic voltammogram recorded at 10 Vs-1, in which 1-electron

oxidation waves of ferrocenyl(ES-EF) and diemthylaminophenyl(ES-AN) were fitted with

Gaussian-Lorenzian curves with linear baseline correction (Igor Pro. 6.22J) . Gas

chromatography(GC) was carried out with Shimadzu GC-2014 equipped with J&W Scientific

DB-35MS capillary column at 300 C. High-pressure liquid chromatography (HPLC) was carried

out with JASCO LC system equipped with COSMOSIL Cholester packed column eluted with

methanol at 40 C.

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2016

Experimental Procedures:

Selective reaction of one-pot ethynyl/azide solution by N2/O2 replacement

Under a nitrogen atmosphere, CuCl2(tmeda) (9.2 mg, 36 mol) and o-terphenyl (85 mg, 370 mol,

as a GC standard) were mixed in MeOH-DME (1:1 v/v, 6 mL) in a Schlenk tube. Oxygen gas was

bubbled through the solution and phenyl acetylene (EB, 480 L, 4.4 mmol) and benzyl azide(AB, 400

L, 3.2 mmol) were added. The atmosphere was replaced by alternate 30sec bubblings of N2 or O2

through the reaction solution, and the products were monitored by a gas chromatography.

Anodic electrolysis of phenylacetylene with Cu catalyst

A two-compartment cell was equipped with a platinum mesh electrode (as a working electrode), an

Ag/AgNO3 reference electrode, and a platinum wire (as a counter electrode in the separated

compartment). nBu4NPF6 (0.7g, 1.8 mmol), CuCl2(tmeda) (27 mg, 0.11 mmol), phenylacetylene

(1.44 mL, 13 mmol) and o-terpheyl(255 mg, 1.1 mmol, as a standard) were dissolved in

MeOH-DME(1:1 v/v, 18 mL). Anodic potential (+0.4 V vs. Ag+/Ag) was applied just after the

addition of TMEDA(15 L, 0.10mmol), and the reaction was monitored by HPLC. An additional

portion of TMEDA was added to the solution when the product formation ceased by the

consumption of TMEDA with protonation.

Reaction of alkyne-modified electrode

Under a nitrogen atmosphere, two-compartment cell or an undivided cell was equipped with an

Ag/AgNO3 reference electrode, and a platinum wire as a counter electrode. The electrolyte solution

containing 0.1 M nBu4NPF6 in MeOH-DME(1:1 v/v) was charged in the cell, and both or one of the

substrates (37 mM ethynylferrocene and 37 mM 4-(N,N-dimethylamino)phenylazide) were added.

A portion of a stock solution of the catalyst was added to be 6.0 mM Cu(tmeda)Cl2 and 5.6 mM

TMEDA. After a brief stirring of the solution, terminal alkyne modified electrode was immersed in

the solution followed by an immediate electric potential application. After a certain duration of the

potential application, the electrode was rinsed with acetone and hexane, and thoroughly washed (20

min) and sonicated (5 min) in dichloromethane. For the detection of immobilized redox species, the

modified electrodes were immersed in an undivided cell containing 0.1 M nBu4NPF6 acetonitrile

solution, and electrochemical measurements were operated with an Ag/AgNO3 reference electrode,

and a platinum wire as a counter electrode. For a reaction monitoring, the modified electrode was

immersed back into the substrate solution again, and the same procedure was repeated.

Figur

O2/N2

CuCl2

re S1. Gas-c

2 replacemen

2(tmeda) (0.0

chromatograp

nt. The start

035 mmol) an

ph changes o

ting solution

nd TMEDA(0

of one-pot G

n was compo

0.035 mmol) i

o-terphe

solvents reactants

Glaser-Hay/C

osed of EB

in 10 ml MeO

enyl butadiyn

CuAAC solut

(4.3 mmol)

OH-DME(1:1

ne

triazole

tion with alt

, AB (3.2 m

1 v/v).

ternate

mmol),

Figure S2. Time-course-dependent formation of 1,4-diphenylbutadiyne from phenylacetylene by the

anodic Glaser-Hay coupling. Additional portions of TMEDA (1equiv. to Cu) were added at the time

indicated with arrows. Half of the anodic charge profile is also shown with a 0.055 mmol offset,

counting that the initial Cu(II) state of the catalyst.

‐0.05

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Time / s

Charge / 2 m

Fd

1,4-

diph

enyl

buta

diyn

e / m

mol

Additional TMEDA

Figur

Work

re S3. A cyc

king electrode

clic voltammo

e: glassy carb

ogram of Cu

on, counter e

u(tmeda)Cl2 i

electrode: Pt w

in 0.1 M nBu

wire, referenc

u4NPF6-MeO

ce electrode: A

OH/DME (1:1

Ag+/Ag.

1 v/v).

Figur

upon

CuCl2

voltam

Coun

FigurnBu4N

re S4. Cyclic

potential ch

2(tmeda) (6.0

mmograms w

nter electrode:

re S5. (a) Cy

NPF6-acetonit

c voltammogr

hange at the

0 mM) and

were recorde

: Pt wire, refe

yclic voltamm

trile. (b) Scan

rams of termi

electrode. Th

TMEDA(5.5

ed in 0.1 M

erence electro

mograms of E

n rate depend

270210120

0.1 V 60180120

-0.6 V 60i

inal alkyne-m

he reaction s

5 mM) in 0

M nBu4NPF6–M

ode: Ag+/Ag.

ES-EF modifie

dence of the a

0 min0 min0 min0 min0 min0 min0 mininitial

modified glass

solution was

.1M nBu4NP

MeCN after

ed electrode w

anodic peak cu

sy carbon ele

composed o

PF6-MeOH-D

rinsing the

with various s

urrent.

ectrode (ES) r

of EF (37 mM

DME(1:1 v/v)

reaction so

scan rates in

eacted

M in),

). The

lution.

0.1 M

Figur

upon

CuCl2

voltam

Coun

FigurnBu4N

re S6. Cyclic

potential ch

2(tmeda) (6.0

mmograms w

nter electrode:

re S7. (a) Cy

NPF6-acetonit

c voltammogr

hange at the

0 mM) and

were recorde

: Pt wire, refe

clic voltamm

trile. (b) Scan

rams of termi

electrode. T

TMEDA(5.5

ed in 0.1 M

erence electro

mograms of E

n rate depend

0.1 V

-0.6 V

inal alkyne-m

The reaction

5 mM) in 0

M nBu4NPF6–M

ode: Ag+/Ag.

S-AN modifie

dence of the a

30 min15 min60 min30 mininitial

modified glass

solution wa

.1M nBu4NP

MeCN after

ed electrode w

anodic peak cu

sy carbon ele

as composed

PF6-MeOH-D

rinsing the

with various s

urrent.

ectrode (ES) r

d of AN (37

DME(1:1 v/v)

reaction so

scan rates in

eacted

mM),

). The

lution.

0.1 M

Figur

reacte

compnBu4N

rinsin

re S8. Cycl

ed upon appli

posed of EF (3

NPF6-MeOH-

ng the reaction

ic voltammog

ication of var

37 mM), AN (

-DME (1:1 v/

n solution. C

grams of the

rious electric

(37 mM), C

/v). Voltamm

ounter electro

-0

-0

-0.

-0.

0 V

terminal alky

potentials for

CuCl2(tmeda)

mograms were

ode: Pt wire,

.3 V

.2 V

.1 V

05 V

V

yne-modified

r 30 min. The

(6.0 mM), an

e recorded in 0

reference ele

glassy carbo

e reaction solu

nd TMEDA (

0.1 M nBu4N

ectrode: Ag+/A

on electrode

ution was

(5.5 mM) in 0

NPF6–MeCN a

Ag.

0.1M

after

Figur

upon

immo

(37 m

v/v).

FigurnBu4N

termin

4-nitr

-MeO

re S9. Cyclic

successive ap

obilized electr

mM), Cu(tmed

re S10. C

NPF6-acetonit

nal alkyne i

rophenylazide

OH-DME (1:1

voltammogr

pplication of

rode. The rea

da)Cl2 (6.0 m

Cyclic volta

trile upon suc

immobilized

e (37 mM),

1 v/v).

ams of immo

-0.05 V (60 m

action solution

mM) and TME

ammograms

ccessive appl

electrode. T

Cu(tmeda)Cl

a

b

obilized speci

min, a) and -0

n was compo

EDA (5.6 mM

of immo

lication of -0.

The reaction

l2 (6.0 mM)

ies recorded i

0.3 V (30 min

osed of EF (37

M) in 0.1M nB

obilized spe

.05 V (30 min

solution wa

and TMEDA

a

b

n 0.1 M nBu4

n, b) on a term

7 mM), ferroc

u4NPF6 -MeO

ecies record

n, a) and -0.3

as composed

A (5.6 mM) i

4NPF6-aceton

minal alkyne

cenylmethyaz

OH-DME (1:

ded in 0.

V (30 min, b

d of EF (37

in 0.1M nBu

nitrile

zide

:1

1 M

b) on a

mM),

u4NPF6

References

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1 Margraf, G.; Bats, J. W.; Wagner, M.; Lerner, H. W., Inorganica Chimica Acta 2005,

358, 1193-1203. 修論のスキームと異なる

2 Angelica Aguilar-Aguilar, Annette D. Allen, Eduardo Pen a Cabrera, Andrei Fedorov,

Nanyan Fu, Huda Henry-Riyad, Jo¨rg Leuninger, Ulrich Schmid, Thomas T. Tidwell,

and Rishi Verma, J. Org. Chem. 2005, 70, 9556-9561. 3 ステップあり。1 ステップ目は別

の文献 3 Alvarez, S.G.; Alvarez, M.T., Synthesis 1997, 413-414 4 Choi, I.; Kim, Y. K.; Min, D. H.; Lee, S. W.; Yeo, W. S., J. Am. Chem. Soc. 2011, 133, 16718-16721 5 Katti, K.V.; Raghuraman, K.; Pillarsetty, N.; Karra,S. R.; Gulotty, R. J.; Mark A.

Chartier, M. A.; Langhoff, C. A., Chem. Mater. 2002, 14, 2436-2438. 6 Baron, A.; Herrero, C.; Quaranta, A.; Charlot, M. F.; Leibl, W.; Vauzeilles, B.;

Aukauloo, A., Inorg. Chem. 2012, 51, 5985−5987. 2 ステップあり。1 ステップ目は別の

文献

7 Leroux, Y. R.; Fei, H.; Noel, J. M.; Roux, C.; Hapiot, P., J. Am. Chem. Soc. 2010, 132

14039-14041. 2 ステップあり。1 ステップ目は別の文献