Supporting Information
Base assisted C-C coupling between carbonyl and polypyridyl ligands
in Ru-NADH type carbonyl complex
Debashis Ghosh,a Takashi Fukushima,a Katsuaki Kobayashi,a Susan Sen,b Susumu
Kitagawa,c Tatsuhisa katod and Koji Tanaka*a
Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017
Table S1. Treatment of different bases on [1.HH]a
Entry Base Amount of base
(equiv.) Product
1 Et3N 6 No product
2 DABCO 6 No product
3 Proton sponge 6 No product
4 PhCOONBu4 3 Base adduct
5 DBN 3 New five membered
metallacycle
aAll the reactions were carried out with 2mM [1.HH](PF6)2 in 5 mL CH3CN.
Figure S1. UV changes of the [Ru(tpy)(pbn)(CO)]2+ complex (1) after addition of various
amount of Na2S2O4.
Figure S2. UV changes of the [Ru(tpy)(pbn)(CO)]2+ complex (1) after irradiation with light
(> 420 nm) in CH3CN:TEOA = 99:1 observed in a) 45 sec and b) 7200 sec.
14 12 10 8 6 4
0.0
0.2
0.4
14 12 10 8 6 4
0.0
0.2
0.4
(ppm)
[1.HH] + PhCOO- at RT
Ab
an
da
nce
[1.HH]
12.92
Figure S3. 1H NMR spectral changes after addition of PhCOONBu4 (red) to
[Ru(tpy)(pbnHH)(CO)]2+ complex [1.HH] (blue).
460 nm
430 nm
a) b)
Figure S4. Visual colour changes of [1.HH] after addition of DBN followed by O2.
Figure S5. 1H NMR spectrum of (a) the reaction mixture after addition of DBN (3 equiv. with
respect to [1.HH]) to [1.HH] followed by DDQ (2 equiv. with respect to [1.HH]) under argon
atmosphere; (b) pure complex 2.
[Ru(tpy)(pbnHH)(CO)]2+
[1.HH]
DBN
Under Ar, RT
O2
Metallacycle
complex 2
After 1 min
After 10 sec
9.5 9.0 8.5 8.0 7.5 7.0 6.5
9.5 9.0 8.5 8.0 7.5 7.0 6.5
b)
(ppm)
Pure complex 2
[1.HH]+DBN+DDQa)
Figure S6. 13C NMR spectrum of (a) the reaction mixture after addition of DBN (3 equiv. with
respect to [1.HH]) to [1.HH] followed by DDQ (2 equiv. with respect to [1.HH]) under argon
atmosphere; (b) pure complex 2. Inset is the 13C NMR spectrum of pure DBN.
260 240 220 200 180 160 140 120
260 240 220 200 180 160 140 120
b)
200 160 120 80 40 0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
(ppm)
Abandance DBN pure
(ppm)
a)
Figure S7. a) Observed ESI-MS spectrum of the metallacycle 2 obtained by the reaction of
[Ru(tpy)(pbnHH)(CO)]2+ with DBN base in CH3CN under air; b) Calculated one.
Figure S8: Cyclic voltammograms (CV) of [Ru(tpy)(pbn)(CO)]2+ (1) in the absence (a) and
presence (b) of 5 equiv. of AcOH, 1mM in Ar-purged CH3CN with 0.1 MBu4NPF6 as the
supporting electrolyte at a scan rate = 50 mVs-1. The curves in the CV were assigned by
comparing with literature data.1,2,3 In the absence of proton (a), 1 undergoes successive one
electron reduction by [pbn]/[pbn-.] and [tpy]/[tpy-.] redox couples. However, in the presence of
proton (b), two electron reduction occurs at the pbn moiety of 1 to form
[Ru(tpy)(pbnHH)(CO)]2+ [1.HH].1,2
b)
a)
C33H21N6ORu
-1.50 -1.25 -1.00 -0.75 -0.50 -0.25
Potential / V vs. SCE
a
b
5A
tpy/tpy.- pbn/pbn.-
tpy/tpy.-
Figure S9. EPR spectrum obtained upon the addition of 3.0 equiv. of DBN to a CH3CN
solution of [1.HH] (1 mM) at 5 K.
Figure S10. EPR spectrum obtained upon the addition of 3.0 equiv. of DBN to a CH2Cl2
solution of [1.HH] (0.5 mM) at 5 K.
1500 2000 2500 3000 3500
g = 2.0081440 1560 1680 1800 1920
Magnetic Field / Gauss
Magnetic Field/Gauss
1500 2000 2500 3000 3500
1440 1560 1680 1800 1920
Magnetic Field / Gauss
Magnetic Field / Gauss
g = 2.008
Figure S11. a) Observed ESI-MS spectrum of the Ru-OCO-bridge complex 3 obtained by the
reaction of metallacycle 2 with 10 equiv. of NH4PF6 in H2O/CH3CN (1:1 v/v) under air; b)
ESI-MS spectrum obtained by the reaction of metallacycle 2 with 10 equiv. of NH4PF6 in
H2O18/CH3CN (1:1 v/v) in presence of molecular oxygen; c) calculated one.
C33H21N6O2Ru
a)
b)
c)
Figure S12. a) Observed ESI-MS spectrum of the Ru-O18CO-bridge complex 3 obtained by
the reaction of metallacycle 2 with 10 equiv. of NH4PF6 in H2O18/CH3CN (1:1 v/v) in presence
of DDQ; c) calculated one.
Figure S13. 1H NMR spectra of (a) [Ru(tpy)(pbn)(CO)]2+ and (b) [Ru(tpy)(pbnHH)(CO)]2+ in
CD3CN.
b
a
10 9 8 7 6 5
10 9 8 7 6 5
(ppm)
(ppm)
b)
a)
Figure S14. 13C NMR spectra of (a) [Ru(tpy)(pbn)(CO)]2+ and (b) [Ru(tpy)(pbnHH)(CO)]2+
in CD3CN.
Figure S15. FT-IR spectra of (a) [Ru(tpy)(pbn)(CO)](PF6)2 (1) and (b) [Ru(tpy)(pbnHH)(CO)]
(PF6)2 [1.HH].
200 150 100 50 0
200 150 100 50 0
(ppm)
b)
a)
2200 2000 1800 1600 1400 1200 1000
60
80
100
b)
Wavenumber/ cm-1
Complex [1.HH]
Complex 1
% T
1988
2000
a)
Figure S16. 1H NMR spectrum of Ru-CO-bridge metallacycle 2 in CD3CN.
Figure S17. 13C NMR spectrum of Ru-CO-bridge metallacycle 2 in CD3CN.
11 10 9 8 7 6 5 4
(ppm)
250 200 150 100 50 0
(ppm)
Figure S18. 1H NMR spectrum of Ru-OCO-bridge complex 3 in CD3CN.
Figure S19. 1H NMR spectrum of Ru-OCO-bridge complex 3 in CD3CN.
11 10 9 8 7 6 5 4
(ppm)
200 150 100 50 0
(ppm)
Figure S20. FT-IR spectra of (a) metallacycle complex 2; (b) complex 3 and (c) complex 1.
References
1. D. E. Polyansky, D. Cabelli, J. T. Muckerman, T. Fukushima, K. Tanaka, and E. Fujita,
Inorg. Chem., 2008, 47, 3958.
2. T. Fukushima, T. Wada, H. Ohtsu and K. Tanaka, Dalton Trans., 2010, 39, 11526.
3. H. Nagao, T. Mizukawa and K. Tanaka, Inorg. Chem., 1994, 33, 3415.
2200 2000 1800 1600 1400 1200 1000
40
60
80
100
120
Wavenumber/ cm-1
% T
c)
b)
a)
Complex 2
Complex 3
Complex 1
2000
1621
1572
