Inorganic Chemistry
Article
Headspace Sampler and 7820A GC System by Agilent Technologies.
The UV-1800 from Shimadzu with 1 cm quartz cuvettes was used for
the UV/vis measurements. Cyclic voltammograms were recorded
using an Autolab PGSTAT101 from Metrohm in MeCN solutions: 10
mL solvent, 1 mM sample, and 100 mM tetrabutylammonium
hexfluorophosphate (nBu N)PF as supporting electrolyte). Solutions
2H, HPYA), 8.55 (d, 3JHH = 5.9 Hz, 2H, HPYA), 8.32 (d, J = 9.0 Hz,
3
HH
3
2H, HPYA), 8.10−8.20 (m, 3H, H ), 8.01 (dd, J = 9.0, 5.9 Hz, 2H,
pyr
HH
HPYA), 4.37 (s, 6H, N−CH ), 2.65 (s, 3H, NCCH ), 2.34 (s, 6H,
3
3
1
3
NCCH3). C NMR (101 MHz, DMSO-d ) δ 169.4 (CO), 153.6
6
(Cpyr), 151.8 (C ), 144.0 (CH ), 143.0 (CH ), 139.9 (CH ),
139.5 (CH ), 127.2 (CH ), 125.3 (CH ), 125.1 (NCMe), 118.1
pyr
pyr
pyr
pyr
4
6
pyr
pyr
pyr
(NCMe), 47.7 (N−CH ), 3.8 (NCCH ), 1.1 (NCCH ). HR-MS: m/
3
3
3
+
z calculated for C H F N O PRu [M − PF ] = 717.0862; found:
2
5
26
6
8
2
6
717.0859. Elemental Analysis: anal. calculated for
C H F N O P Ru: C: 34.85, H: 3.04, N: 13.01. Found: C:
2
5
26 12
8
2 2
+
35.50, H: 3.63, N: 12.50.
General Procedure for the Synthesis of Complexes 2b−f.
Compound 2a (1.0 equiv) and the indicated ligand were dissolved in
EtOH (50 mL) and heated to reflux at 90 °C for 16 h. The mixture
was cooled to rt and evaporated to dryness. The residue was dissolved
in a minimum amount of MeCN and precipitated by addition of
Et O. The precipitate was filtered, and washed with Et O, and dried in
2
2
vacuo to yield the title complex as a crystalline powder.
washed with water and Et O and dried under reduced pressure to give
L1 as colorless needle-like crystals (1.564 g, 96%). H NMR (300
Complex 2b. This complex was synthesized according to the
general procedure from 2a (97 mg, 0.113 mmol, 1.0 equiv) and 1,1-
bis(diphenylphosphino)methane (92 mg, 0.120 mmol). Compound
2
1
3
MHz, DMSO-d ) δ 11.95 (s, 2H, NH
), 8.87 (d, J = 7.4 Hz,
6
amide
HH
3
1
4
H, HPYA), 8.56−8.58 (m, 2H, H ), 8.49 (d, J = 7.4 Hz, 4H,
2b was obtained as orange crystalline powder (106 mg, 79%). H
pyr
HH
1
3
HPYA), 8.44−8.50 (m, 1H, H ), 4.26 (s, 6H, N−CH ). C NMR
NMR (400 MHz, MeCN-d ) δ 8.35−8.39 (m, 1H, Hpyr), 8.27−8.29
3
pyr
3
(
101 MHz, DMSO−d ) δ 163.3 (CO), 150.8 (C ), 147.2 (C ),
(m, 2H, Hpyr), 7.75 (s, 1H, HPYA), 7.73 (s, 1H, HPYA) 7.44−7.46 (m,
2H, HPYA), 7.43−7.37 (m, 4H, HPh), 7.30−7.34 (m, 2H, HPYA), 7.27−
7.18 (m, 8H, HPh), 7.16−7.05 (m, 8H, HPh), 6.94−6.98 (m, 2H,
6
pyr
pyr
1
46.2 (CH ), 141.0 (CH ), 127.3 (CH ), 116.0 (CH ), 46.7
pyr pyr pyr pyr
+
(
N−CH ). ESI MS (CH CN) m/z: 494.12 [M − PF ] , 348.15 [M −
3
3
6
+
+
2
2
2
PF − H] . HR-MS: m/z calculated for C H O N F P [M−PF ]
H
PYA), 4.72 (d, JHH = 10.1 Hz, 1H, CH
2
), 4.69 (d, JHH = 10.1 Hz,
6
19 19
2
5
6
6
1
3
=
494.1151; found: 494.1175. Elemental Analysis: Anal. Calculated
1H, CH
2
), 3.85 (s, 6H, N−CH
170.3 (CO), 154.6 (Cpyr), 152.5 (Cpyr), 143.8 (CHpyr), 143.2 (CHpyr),
139.7 (CHpyr), 139.2 (CHpyr), 134.7 ( JCP = 37 Hz, JCP = 4.2 Hz,
CPh), 134.3 ( JCP = 33 Hz, JCP = 3.6 Hz, CPh), 132.1 (JCP = 11.2 Hz,
3
). C NMR (101 MHz, MeCN-d ) δ
3
for C H F N O P : C: 35.70; H: 3.00; N: 10.95. Found: C: 35.63;
19
19 12
5
2 2
1
3
H: 3.85; N: 10.69.
1
3
Compound L2. This product was prepared according to the same
procedure as described for L1 from the iodide salt X2 (1.808 g, 3.0
mmol) in MeCN (50 mL) and NH PF (2.458 g, 15.0 mmol) in H O
CHPh), 131.8 (JCP = 2.6 Hz, CHPh), 131.4 (JCP = 10.3 Hz, CHPh),
131.2 (JCP = 2.4 Hz, CHPh), 130.4 (JCP = 10.0 Hz, CHPh), 129.9 (JCP
4
6
2
1
(
100 mL), which afforded L2 as colorless crystals (1.863 g, 97%). H
= 9.7 Hz, CHPh), 128.0 (CHpyr), 127.1 (CHpyr), 48.9 (N−CH
3
), 43.0
) δ 0.14
3
1
31
1
NMR (300 MHz, DMSO-d ) δ 11.67 (s, 2H, NHamide), 9.72 (s, 2H,
(t, JCP = 26 Hz, CH
2
). P{ H} NMR (162 MHz, MeCN−d
6
3
3
2
2
HPYA), 8.85 (d, J = 8.6, 2H, HPYA), 8.82 (d, J = 6.0, 2H, HPYA),
(d, JPP= 57.8 Hz, 1P, dppm), − 3.24 (d, JPP = 57.8 Hz, 1P, dppm),
HH
HH
3
1
8
8
.53−8.55 (m, 2H, H ), 8.43−8.47 (m, 1H, H ), 8.23 (dd, J
=
− 144.59 (hept, JPF = 708 Hz, 2P, PF
Ru [M − PF − MeCN] = 978.1259; found
978.1259. Elemental Analysis: anal. calculated for
Ru × H O: C: 46.75, H: 3.75, N: 7.11. Found:
C: 46.70, H: 4.13, N: 6.90.
6
). HR-MS: m/z calculated for
pyr
pyr
HH
1
3
+
.6, 6.0 Hz, 2H, H ), 4.47 (s, 6H, N−CH ). C NMR (101 MHz,
C
H
44
O
39
N
2
5
F
6
P
3
6
PYA
3
DMSO−d ) δ 162.4 (CO), 147.3 (C ), 141.1 (CHpyr), 141.0
6
pyr
(
CH ), 137.9 (C ), 136.4 (CH ), 135.1 (CH ), 127.9 (CH ),
C
H
46
F
42
N
12
O
6
P
2
4
2
pyr
pyr
pyr
pyr
pyr
1
26.6 (CH ), 48.7 (N−CH ). ESI MS (CH CN) m/z: 494.12 [M −
pyr
3
3
2+
PF ] , 174.58 [M−2 PF ] . Elemental Analysis: Anal. Calculated for
C H F N O P : C: 35.70; H: 3.00; N: 10.95. Found: C: 35.66; H:
Complex 2c. This complex was synthesized according to general
procedures with compound 2a (117 mg, 0.136 mmol, 1.0 equiv) and
1,2-bis(diphenylphosphino)ethane (56 mg, 0.141 mmol, 1.0 equiv).
6
+
6
19
19 12
5
2 2
3
.00; N: 10.89.
Complex 1. A solution of L1 (130 mg, 0.20 mmol), [RuCl (cym)]
Compound 2c was obtained as orange crystalline powder (137 mg,
2
2
1
(
60 mg, 0.10 mmol), and Na CO (65 mg, 0.60 mmol) in MeCN (50
0.116 mmol, 99% yield). H NMR (300 MHz, DMSO-d
6
) δ 8.50 (t,
2
3
3
3
3
mL) was stirred at reflux for 16 h. The reaction mixture changed color
from orange to deep red. After cooling to rt, the reaction mixture was
filtered over Celite, and the red solution was concentrated under
JHH = 7.8 Hz, 1H, Hpyr), 8.26 (d, JHH = 7.8 Hz, 2H, Hpyr), 8.06 (d,
JHH = 6.9 Hz, 2H, HPYA), 7.66 (s, 2H, HPYA), 7.31 (dd, J = 6.9, 8.4
3
HH
Hz, 2H, H ), 7.28−7.16 (m, 14H, H ), 7.06−7.02 (m, 6H, H ),
PYA
Ph
Ph
3
reduced pressure to 5 mL. Addition of Et O (100 mL) gave a dark red
6.81 (d, J = 8.4 Hz, 2H, H ), 3.98 (s, 6H, N−CH ), 3.06 (br m,
2
HH
PYA
3
13
precipitate which was collected by filtration and redissolved in MeCN
2H, P−CH ), 2.81 (br m, 2H, P−CH ). C NMR (101 MHz,
2
2
(
10 mL), filtered over Celite, and precipitated again by addition of
DMSO−d ) δ 170.5 (CO), 154.1 (Cpyr), 150.8 (Cpyr), 142.9 (CH ),
6
pyr
1
Et O (100 mL). The product was collected by filtration and drying of
140.5 (CH ), 139.5 (CH ), 138.2 (CH ), 134.9 ( J = 36 Hz,
2
pyr pyr pyr CP
the residue under reduced pressure yielded the complex as a red-
C ), 130.8 (CH ), 130.2 (J = 8.1 Hz, CH ), 128.9 (J = 9.5 Hz,
Ph pyr CP Ph CP
CH ), 128.2 (J = 8.9 Hz, CH ), 126.7 (CH ), 114.5 (NCMe),
Ph CP Ph pyr
31
1
brown powder 1 (157 mg, 91%). H NMR (300 MHz, DMSO-d ) δ
6
3
8
.52 (d, J = 7.3 Hz, 4H, HPYA), 8.19−8.21 (m, 3H, Hpyr), 7.91 (d,
47.4 (N−CH ), 24.0 (P−CH ), 22.0 (P−CH ), 1.1 (NCCH ).
P
HH
3
2
2
3
3
3
JHH = 7.3 Hz, 4H, HPYA), 4.13 (s, 6H, N−CH ), 2.76 (s, 3H,
NMR (162 MHz, DMSO-d ) δ 66.23 (d, J = 13.8 Hz, 1P,dppe),
3
6 PP
1
3
3
1
NCCH ), 2.34 (s, 6H, NCCH ). C NMR (101 MHz, DMSO-d ) δ
54.25 (d, JPP = 13.8 Hz, 1P, dppe), − 144.17 (hept, JPF = 711 Hz,
2P, PF ). HR-MS: m/z calculated for C45 Ru [M − PF
− MeCN] = 992.1415; found: 992.1430. Elemental Analysis: anal.
calculated for C47 Ru × H O: C: 47.21, H: 3.88, N:
7.03. Found: C: 47.19, H: 4.29, N: 6.79.
3
3
6
1
1
70.9 (CO), 164.3 (Cpyr), 153.9 (Cpyr), 144.1 (CH ), 139.1 (CH ),
6
H
41
O
2
N
5
F
6
P
3
6
pyr
pyr
+
30.8 (NCMe), 128.1 (CH ), 122.7 (CH ), 118.1 (NCMe), 45.9
pyr
pyr
(
N−CH ), 4.7 (NCCH ), 1.1 (NCCH ). HR-MS: m/z calculated for
H
44
F
12
N
6
O
2
P
4
2
3
3
3
+
C H O N F PRu [M − PF − MeCN] = 676.0590; found:
6
23
23
2
7
6
6
76.0593. Elemental Analysis: anal. calculated for
Complex 2d. This complex was synthesized according to general
procedures with compound 2a (96 mg, 0.111 mmol, 1.0 equiv) and
triphenylphosphine (31 mg, 0.118 mmol, 1.0 equiv). Compound 2d
C H F N O P Ru: C: 34.85; H: 3.04; N: 13.01. Found: C:
25
26 12
8
2 2
3
4.86; H: 3.02; N: 12.71.
Complex 2a. This complex was synthesized according to the same
was obtained as red crystalline powder (100 mg, 0.077 mmol, 66%
1
procedure as described for complex 1 starting from L2 (419 mg, 0.645
yield). H NMR (400 MHz, MeCN−d
3
) δ 8.33 (s, 2H, HPYA), 8.24
3
3
mmol), [RuCl (cym)] (201 mg, 0.335 mmol), and Na CO (218 mg,
(d, JHH = 8.5, 2H, HPYA), 8.18 (d, JHH = 6.0, 2H, HPYA), 7.88 (dd,
HH = 8.5, 6.0 Hz, 2H, HPYA), 7.76 (t, JHH = 7.7 Hz, 1H, Hpyr), 7.60
(d, J = 7.7 Hz, 2H, H ), 7.24−7.28 (m, 3H, H ), 6.99−7.04 (m,
2
2
2
3
3
3
2
.0 mmol) in MeCN (150 mL) and was obtained as a red crystalline
J
1
3
powder (505 mg, 96%). H NMR (300 MHz, DMSO-d ) δ 9.07 (s,
6
HH
pyr
Ph
K
Inorg. Chem. XXXX, XXX, XXX−XXX