R.J. Sullivan et al. / Polyhedron xxx (2015) xxx–xxx
3
total reaction solution volume of 25 mL the reactor had a gas-
phase headspace of ꢁ50 mL (unused reactor body plus enclosed,
pressurized magnet-drive assembly). Unless otherwise specified
the tail of the orange-red band that eluted yielded 3a, after removal
of the solvent, as an orange powder in good purity. 1H NMR:
3
(400 MHz, MeCN-d , d): 9.62 (d, J = 5.4 Hz, 1H), 8.83 (s, 2H), 8.63
(
cf. control experiments) the reactor vessel and impeller were
(d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.0 Hz, 2H), 8.37 (d, J = 8.1 Hz, 1H),
8.33 (t, J = 7.8 Hz, 1H), 8.13 (d, J = 7.3 Hz, 2H), 8.03 (t, J = 7.8 Hz,
2H), 7.98 (t, J = 6.2 Hz, 1H), 7.81 (t, J = 8.7 Hz, 1H), 7.73
cleaned and polished after each reaction using 3 M abrasive pads
or a sand blaster, respectively.
(
t, J = 7.1 Hz, 2H), 7.71 (d, J = 4.5 Hz, 2H), 7.66 (t, J = 7.3 Hz, 1H),
0
13
2
.2. Chloro(bipy)(4 -Ph-terpy) ruthenium(II) hexafluorophosphate
3
7.36 (m, 3H), 7.09 (t, J = 6.2 Hz, 1H). C NMR: (100 MHz, MeCN-d ,
d): 159.34 (C), 158.54 (C), 158.51 (C), 156.80 (C), 154.10 (CH),
153.35 (CH), 152.01 (CH), 150.22 (C), 139.40 (CH), 138.52 (CH),
138.27 (CH), 137.47 (C), 131.41 (CH), 130.50 (CH), 128.73 (CH),
128.67 (CH), 128.41 (CH), 127.54 (CH), 126.03 (C), 125.32 (CH),
The procedure reported by Rasmussen et al. for the analogous
0
[
RuCl(bipy)(4 -Ph-terpy)](PF
6
) was followed substituting phterpy
0
0
3
for terpy [10]. RuCl (4 -Ph-terpy) (0.501 g, 0.968 mmol), 2,2 -bipyr-
2+
idine (0.167 g, 1.07 mmol) and LiCl (0.204 g, 4.81 mmol) were sus-
pended in 3:1 EtOH:H (100 mL). Triethylamine (1.0 mL,
.0 mmol) was added and the mixture was purged with Ar for
0 min then refluxed under Ar for 4 h. The deep red-purple solu-
125.05 (CH), 124.43 (CH), 122.37 (CH). ESI-MS: [M]
304.02; calc. [C33H N Ru] : 304.06.
26 6
peak:
2
+
2
O
7
1
0
2.4. Chloro(4 -Ph-terpy)(8-quinolinethiolate) ruthenium(III) chloride
tion was cooled to room temperature, filtered then concentrated
to half volume and added to 100 mL of saturated, aqueous KPF
The resulting red-purple ppt. was collected via filtration, washed
O (50 mL). The product was
purified by column chromatography (neutral alumina, Brockmann
activity I stationary phase, 25 ꢂ 300 mm column, 1:1 acetone:-
toluene eluent). The desired product eluted first as a dark purple
band that was collected and evaporated to yield a purple residue.
6
.
The following was performed with the exclusion of O
2
using
0
3
standard Schlenk techniques. RuCl (4 -Ph-terpy) (0.498 g,
with 4 ꢂ 10 mL cold 3 M HCl then Et
2
0.964 mmol), 8-quinolinethiol hydrochloride (0.228 g, 1.15 mmol)
and sodium bicarbonate (0.194 g, 2.31 mmol) were suspended in
methanol (150 mL) and refluxed overnight. The resulting dark
red solution was cooled to room temperature and filtered. The sol-
vent was removed in vacuo yielding the product as a red powder.
Yield 0.599 g; 97%. Small amounts of impurities were present;
2
The residue was dissolved in minimal acetonitrile, added to Et O
+
(
200 mL) and the resulting purple powder was collected by filtra-
the product was used without further purification. ESI-MS: M
1
+
tion and washed with Et
2
O. Yield: 0.462 g; 64%.
= 5.6 Hz, J = 0.7 Hz, 1H),
.10 (s, 2H), 8.93 (d, J = 8.1 Hz, 1H), 8.87 (d, J = 7.9 Hz, 2H), 8.65
d, J = 8.0 Hz, 1H), 8.44 (dt, J = 7.9 Hz, J = 1.5 Hz, 1H), 8.26
d, J = 7.1 Hz, 2H), 8.14 (ddd, J = 7.1 Hz, J
= 1.5 Hz, 2H), 7.89 (dd, J
H
NMR:
peak: 605.9; calc. [C30
H21ClN
4
SRu] : 606.02.
(
9
(
(
1
400 MHz, acetone-d
6
, d): 10.41 (dd, J
1
2
0
2.5. Acetonitrile(4 -Ph-terpy)(8-quinolinethiolate) ruthenium(II)
1
2
triflate (4)
1
2
= 5.6 Hz, J
3
= 1.3 Hz,
= 5.5 Hz,
0
H), 8.03 (dt, J
1
= 7.9 Hz, J
2
1
[RuCl(quS)(4 -Ph-terpy)]Cl (0.481 g, 0.750 mmol), silver triflate
J
7
J
J
1
1
(
1
1
2
= 0.7 Hz, 2H), 7.85 (dt, J
1
= 7.6 Hz, J
2
= 0.9 Hz, 1H), 7.71 (t, 2H),
(1.03 g, 4.01 mmol) and zinc powder (0.496 g, 7.69 mmol) were
suspended in acetonitrile (150 mL) and refluxed under argon over-
night resulting in a deep red solution and off white precipitate. The
mixture was cooled to room temperature and filtered. The insoluble
materials were discarded. The solvent was removed from the fil-
trate in vacuo resulting in a dark burgundy residue that was purified
by column chromatography (neutral alumina, Brockmann activity I
stationary phase, 25 ꢂ 300 mm column, 1:1 MeCN:toluene eluent).
The product eluted first as a dark red band that was collected and
.70 (d, 1H), 7.64 (t, J = 7.3 Hz, 1H), 7.44 (ddd,
= 5.5 Hz, = 1.3 Hz, 2H), 7.14 (ddd, = 7.3 Hz,
= 1.3 Hz, 1H). C NMR: (100 MHz, acetone-d
J
J
1
= 7.6 Hz,
= 5.8 Hz,
2
J
3
J
1
2
1
3
3
6
, d): 160.67 (C),
60.52 (C), 159.88 (C), 157.94 (C), 154.27 (CH), 153.86 (CH),
53.68 (CH), 147.48 (C), 138.66 (C), 138.45 (CH), 138.18
CH), 137.12 (CH), 131.49 (CH), 130.99 (CH), 129.17 (CH),
28.88 (CH), 128.42 (CH), 127.91 (CH), 125.40 (CH), 125.10 (CH),
+
23
24.92 (CH), 121.73 (CH). ESI-MS: M peak: 602.07; calc. [C31H -
+
ClN
5
Ru] : 602.07.
evaporated yielding a dark burgundy solid that was stored under
1
argon. Yield: 0.254 g; 44%. H NMR: (400 MHz, MeCN-d
3
, d): 9.66
0
2
.3. (Bipy)(4 -Ph-terpy)(triflato) ruthenium(II) trifilate (3)
(dd, J
H), 8.40 (dd, J
7.94 (t, J = 8.0 Hz, 2H), 7.81 (d, J = 5.4 Hz, 2H), 7.70 (dd, J
= 5.0 Hz, 1H), 7.65 (t, J = 7.6 Hz, 2H), 7.59 (t, J = 7.2 Hz, 1H), 7.50
(d, J = 7.9 Hz, 1H), 7.42 (d, J = 7.1 Hz, 1H), 7.33 (t, J = 6.3 Hz, 2H),
1
= 5.1 Hz, J
2
= 1.4 Hz, 1H), 8.63 (s, 2H), 8.50 (d, J = 7.9 Hz,
= 8.4 Hz, J = 1.2 Hz, 1H), 8.06 (d, J = 7 Hz, 2H),
= 8.3 Hz,
2
1
2
The procedure reported by Rasmussen et al. for the analogous [Ru
1
0
(
OTf)(bipy)(4 -Ph-terpy)](OTf) was followed with slight modifica-
J
2
tion [10]. The following was performed with the exclusion of O
using standard Schlenk technique. [RuCl(bipy)(4 -Ph-terpy)](PF
2
0
13
6
)
3
7.28 (t, J = 7.7 Hz, 1H), 2.01 (s, 3H). C NMR: (100 MHz, MeCN-d ,
(
(
8
0.417 g, 0.558 mmol) was dissolved in 1,2-dichlorobenzene
50 mL) forming a dark purple solution. Triflic acid (0.75 mL,
.5 mmol) was added resulting in an immediate color change to dark
cherry red. The solution was stirred for 4 h at 50 °C then cooled to
O (200 mL). The resulting solid was fil-
d): 159.66 (C), 159.15 (C), 154.01 (C),153.01 (CH), 152.80 (C),
152.32 (CH), 146.93 (C), 137.94 (C), 137.89 (CH), 137.50 (CH),
132.24 (C), 130.80 (CH), 130.73 (CH), 130.28 (CH), 128.41 (CH),
128.15 (CH), 127.93 (CH), 124.39 (CH), 122.91 (CH), 121.07 (C),
+
0
°C and added to ꢀ20 °C Et
2
120.08 (CH), 120.67 (CH), 4.11 (CH
571.0523; calc. [C30H N SRu] : 571.0525.
21 4
3
). ESI-TOF-MS: [M-MeCN] :
+
tered and washed with Et
powder. The product was contaminated with 9% [Ru(4 -Ph-terpy)
2
O. Yield: 0.380 g; 79% dark cherry red
0
2
]
(
OTf)
2
by mass but was used as is for catalysis experiments since the
2.6. Computations
0
catalytic activity of [Ru(4 -Ph-terpy)
2 2
](OTf) was previously deter-
mined to be negligible. NMR and mass spectra were collected in ace-
tonitrile after allowing 2 h at room temperature for replacement of
All calculations were performed using the GAUSSIAN 09 software
suite [11]. All structures were optimized using the M06-L func-
tional [12,13], with def2-SVP basis set [14] and associated ECP
[15] for Ru and 6-31G(d,p) basis set [16–18] for all other atoms.
An ultrafine integration grid (99 radial shells with 590 angular
points per shell) was used. Solvent effects were incorporated using
the polarizable continuum model for water [19–23]. All structures
were verified to be local minima or transition states by frequency
the highly labile triflate by acetonitrile in the sixth coordination site.
0
High purity samples of [Ru(NCMe)(bipy)(4 -Ph-terpy)](OTf)
2
(3a)
for characterization were produced in low yield (ꢁ1%) using column
chromatography (alumina neutral, Brockmann activity I,
0
2
0 ꢂ 300 mm, 2:1 MeCN:toluene eluent). The separation of [Ru(4 -
2 2
Ph-terpy) ](OTf) and 3a was minimal, however collecting only