Full Paper
–
+
them to float by a factor of +/–1.25, whereas ν was constrained (754.11, [{Ru(dmb) (1)} + PF ] , C H F N PRuS, 34 %), 799.09
L
2
6
31 33 6 5
–
1
+
– +
between 400–500 cm and S between 0–4, as seen for other diim-
(799.16, [{Ru(dmb) (1) – H} + 2Na + PF ] , C H F N Na PRuS,
L
2 6 31 32 6 5 2
[14,22]
ine complexes in the literature.
-(Methylthiomethyl)pyridine (1): 2-(Mercaptomethyl)pyridine
15.5 g, 0.12 mol) and Et N (1.1 equiv., 0.13 mol, 13.8 g, 19.2 mL)
100 %). C H F N OP RuS (956.78): calcd. C 42.68, H 4.11, N 8.94;
34 39 12 5 2
found C 42.97, H 3.68, N 8.18.
2
(
[Ru(phen) (1)](PF ) : Prepared analogously to [Ru(bpy) (1)](PF )
6 2
3
2
6 2
2
were dissolved in MeCN (25 mL) and cooled to 0 °C whereupon a but by using 1,10-phenanthroline to give an orange powder
solution of MeI (1.1 equiv., 0.13 mol, 19.4 g, 8.5 mL) in MeCN (20 mL)
was added dropwise. The reaction mixture was allowed to slowly
warm to room temperature and stirred overnight whereupon the
(132.0 mg, 0.15 mmol, 70.6 %). Recrystallization from acetone gave
X-ray quality single crystals. FTIR (ATR diamond anvil): ν = 1427 (w),
˜
–
1
835 (s, br), 776 (w), 722 (w), 556 (m) cm . MS (ESI, MeCN, pos.
solvent was evaporated under reduced pressure leading to a mix- mode): calcd. (found) m/z = 321.05 (321.05, [{Ru(phen) (1)} + H O
2
2
+
2+
ture of 2-(methylthiomethyl)pyridine and triethylamine hydroiod- + Na ] , C H N NaORuS, 98 %), 497.06 (497.01, [{Ru(phen)(1)} +
H O + MeCN + OH ] , C H N O RuS, 100 %), 515.07 (515.02,
remove Et N·HI. The solvent was evaporated under reduced pres- [{Ru(phen)(1)} + 2H O + MeCN + OH] , C H N O RuS, 74 %),
3
1 27 5
–
+
ide. The mixture was triturated with EtOAc (100 mL) and filtered to
2 21 23 4 2
+
3
2
21 25 4 3
–
+
sure to give a yellow oil, which was dissolved in CH Cl (100 mL)
787.08 (787.07, [{Ru(phen) (1)} + MeCN + PF ] , C H F N PRuS,
2
2
2 6 33 28 6 6
and washed with dilute aqueous NaOH (50 mL, 0.4
M). The organic
78 %). C H F N P RuS (890.64): calcd. C 41.81, H 2.83, N 7.86;
31 25 12 5 2
phase was separated, dried with MgSO , and evaporated to yield
found C 42.46, H 2.69, N 7.66.
4
2
-(methylthiomethyl)pyridine as a clear liquid, which was further
[
Ru(tpa)(1)](PF ) : Prepared analogously to [Ru(bpy) (1)](PF ) but
6
2
2
6 2
1
purified by vacuum distillation (12.10 g, 0.09 mol, 70.10 %). H NMR
400 MHz, CDCl ): δ = 8.49 (dq, J = 4.9 Hz, 1 H), 7.61 (td, J = 7.7,
by using tris(2-pyridylmethyl)amine to give an olive-green powder
138.2 mg, 0.17 mmol, 80.2 %). Recrystallization from acetone gave
X-ray quality single crystals. FTIR (ATR diamond anvil): ν˜ = 1606 (w),
480 (w), 1448 (m), 1161 (w), 992 (w), 829 (s), 768 (s), 558 (s), 508
(
3
(
1
1
1
.9 Hz, 1 H), 7.31 (ddd, J = 7.8, 4.8, 1.2 Hz, 1 H), 7.11 (t, J = 7.2 Hz,
1
3
H), 3.75 (s, 2 H), 2.01 (s, 3 H) ppm. C NMR (100 MHz, CDCl ): δ =
3
1
58.62, 149.29, 136.69, 123.00, 121.89, 40.10, 15.17 ppm.
–1
(m) cm . MS (ESI, MeCN, pos. mode): calcd. (found) m/z = 258.04
–
2+
2
-(Ethylthiomethyl)pyridine (2): Synthesized analogously to com-
(258.04, [Ru(tpa)(1
(265.55, [Ru(tpa)(1)] , C H N RuS, 43 %), 550.09 (550.10,
[Ru(tpa)(1 – CH ) + 2OH ] , C H N O RuS, 100 %), 676.07
3 24 26 5 2
–
CH )] , C H N RuS, 72 %), 265.55
3 24 24 5
2
+
pound 1 but by using ethyl iodide. Purified by short-path vacuum
distillation to yield a colorless liquid (42.8 %). H NMR (400 MHz,
CDCl ): δ = 8.47 (d, J = 5.0 Hz, 1 H), 7.59 (td, J = 7.7, 1.8 Hz, 1 H), (676.06, [{Ru(tpa)(1)} + PF ] , C H F N PRuS, 19 %), 736.08
25 27 5
– +
1
–
–
+
3
6
25 27 6 5
–
–
– +
7
.32 (d, J = 7.1 Hz, 1 H), 7.10 (ddd, J = 7.5, 4.9, 1.2 Hz, 1 H), 3.79 (s,
(736.13, [Ru(tpa)(1
C H F N O PRuS,17 %). C H F N P RuS (820.59): calcd. C 36.59,
–
CH )
+
MeCN
+
2OH
+ PF ] ,
3
6
2
H), 2.46 (q, J = 7.4 Hz, 2 H), 1.18 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR
26
29
6
6
2
25 27 12 5 2
(
100 MHz, CDCl ): δ = 159.02, 149.23, 136.66, 123.00, 121.81, 38.83,
H 3.32, N 8.53; found C 37.00, H 3.15, N 8.55.
3
2
5.61, 14.45 ppm.
[
Ru(1) ](ClO ) ·H O: [RuCl (dmso) ] (345.2 mg, 0.71 mmol) and 2-
3
4 2
2
2
4
[
2
Ru(bpy) (1)](PF ) : [RuCl (dmso) (1)] (100.0 mg, 0.21 mmol) and
,2′-bipyridine (66.8, 0.43 mmol, 2 equiv.) were suspended in glyc-
(methylthiomethyl)pyridine (300.0 mg, 2.14 mmol, 3 equiv.) were
dissolved in abs. EtOH (75 mL). AgNO3 (255.6 mg, 1.50 mmol,
2.1 equiv.) was added and the reaction mixture was heated at reflux
for 2 h followed by stirring at room temperature for 48 h. The pre-
cipitated AgCl was removed by filtration through Celite and the
solvent was removed in vacuo to give an orange oil, which was
2
6 2
2
2
erol (10 mL) and the reaction mixture was irradiated in a microwave
at 200 °C for 20 min. The resulting dark-red solution was immedi-
ately poured over ice-cold saturated aqueous NH PF (5 mL). The
4
6
precipitate was collected by centrifugation, re-suspended in H O
2
(
5 mL) followed by filtration and additional washing with H O
dissolved in H O (15 mL). The product was precipitated by the slow
2
2
(
5 mL) to remove residual NH PF . To remove residual glycerol the addition of a saturated aqueous solution of NaClO , collected by
4
6
4
product was purified by dissolution in CH CN followed by careful
filtration, and washed with ice-cold H O (3 × 5 mL) to give a tan-
3
2
addition of EtOH. The product was precipitated at –40 °C and fil-
yellow powder after drying (220.0 mg, 0.29 mmol, 42.1 %). FTIR (ATR
tered through a glass frit funnel, washed with abs. EtOH, and air- diamond anvil): ν˜ = 1603 (w), 1473 (w), 1435 (m), 1075 (s, br), 975
–
1
dried to give the product as a red/brown powder to give a red-
orange powder (138.2 mg, 0.16 mmol, 78.1 %). FTIR (ATR diamond
(m), 767 (m), 753 (m), 623 (s) cm . MS (ESI, MeCN, pos. mode):
2
+
calcd. (found) m/z
=
252.01 (252.01, [{Ru(1) }
–
CH ] ,
3
3
–1
2+
anvil): ν˜ = 1466 (w), 1447 (w), 836 (s), 763 (m), 732 (w), 557 (m) cm .
C H N RuS , 100 %), 259.52 (259.52, [Ru(1) ] , C H N RuS ,
20 24 3 3 3 21 27 3 3
+
MS (ESI, MeCN, pos. mode): calcd. (found) m/z = 269.03 (269.03,
75 %), 348.94 (348.94, [{Ru(1 – CH ) } – H] , C H N RuS , 9 %),
3
2
12 11
2
2
2
+
+
[
[
Ru(bpy) (1
–
CH )] , C H F N P, 60 %), 276.55 (276.54,
363.96 (363.97, [{Ru(1)(1 – CH )} – H] , C H N RuS , 37 %), 478.94
2
3
27 25 12
5
3 13 14 2 2
2
+
3+
– +
Ru(bpy) (1)] , C H N RuS, 20 %), 285.05 (285.05, [{Ru(bpy) (1)}
(478.94, [{Ru(1) } + ClO ] , C H ClN O RuS , 12 %), 501.93
2 4 14 18 2 4 2
2
2+
27 25
5
2
–
–
+ +
+
CH3)}
OH ] , C H N RuSO, 100 %), 572.07 (572.08, [{Ru(bpy) (1 – (502.02, [{Ru(1) } + ClO4 + Na ] , C H ClN NaO RuS , 6 %), 517.93
27
26
5
– +
2
2
14 18
+
2
4
2
3+
–
+
+
2OH ] , C H N O2, 22 %), 698.05 (698.04,
(518.03, [{Ru(1) } + ClO4 + Na + O] , C H ClN NaO RuS , 5 %),
26
24
5
2
14 18
2
5
2
2+
– +
–
–
+
– +
[
[
{Ru(bpy) (1)} + PF ] , C H F N PRuS, 27 %), 715.05 (715.07, 617.88 (617.99, [{Ru(1)2}
+
ClO4
+
Na
+
OH ] ,
2
6
27 25 6 5
– +
{Ru(bpy) (1)}
+
OH
+
PF ] , C H F N OPRuS, 66 %).
C H Cl N NaO RuS , 6 %). C H Cl N O RuS (735.63): C 34.29, H
14 19 2 2 9 2 21 29 2 3 9 3
2
6
27 26
6
5
C H F N P RuS (842.59): calcd. C 38.49, H 2.99, N, 8.31; found C
3.97, N 5.71; found C 33.91, H 3.38, N 5.62.
Ru(2) ](ClO ) ·H O: [RuCl (dmso) ] (309.9 mg, 0.64 mmol) and 2-
2
7 25 12 5 2
3
9.88, H 2.69, N 8.89.
[
3
4 2
2
2
4
[
Ru(dmb) (1)](PF ) ·(CH ) CO:
Prepared
analogously
to
(ethylthiomethyl)pyridine (294.0 mg, 1.92 mmol, 3 equiv.) were dis-
solved in abs. EtOH (50 mL). AgNO3 (228.3 mg, 1.34 mmol,
2.1 equiv.) was added and the reaction mixture was heated at reflux
for 2 h followed by stirring at room temperature for an additional
48 h. The precipitated AgCl was removed by filtration through Celite
and the solvent was removed in vacuo to give a red oily mass,
2
6 2
6 2
3 2
[Ru(bpy) (1)](PF ) but by using 4,4′-dimethyl-2,2′-bipyridine to give
2
the product as an orange powder (153.5 mg, 0.16 mmol, 76.4 %).
Recrystallization from acetone gave X-ray quality single crystals.
FTIR (ATR diamond anvil): ν˜ = 1618 (m), 1480 (w), 1239 (w), 820 (s,
–
1
br), 554 (s), 526 (m) cm . MS (ESI, MeCN, pos. mode): calcd. (found)
2
+
m/z = 297.07 (297.06, [Ru(dmb) (1 – CH )] , C H N RuS, 20 %),
3
which was dissolved in H O (10 mL). The product was precipitated
2
3
30 30
5
2
2
+
04.58 (304.57, [Ru(dmb) (1)] , C H N RuS, 18 %), 327.06 (327.10,
by the addition of a saturated aqueous solution of NaClO , collected
2
31 33
5
4
+
2+
[{Ru(dmb) (1) – H} + 2Na ] , C H N Na RuS, 88 %), 754.11
by filtration, washed with H O (2 × 5 mL), and air-dried (323.7 mg,
2
31 32
5
2
2
Eur. J. Inorg. Chem. 2016, 897–906
www.eurjic.org
905
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim