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[(h6-p-Cymene)Ru(1-hydroxy-3-methylpyridine-2(1H)-thionato)Cl]
(1b): Yield: 52% (135 mg), red solid. H NMR (500 MHz, CDCl3): d=
was collected by filtration and washed with diethyl ether. The
yellow-orange solids was left to dry at 458C overnight.
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[(h6-p-Cymene)Ru(1-hydroxypyridine-2(1H)-thionato)pta]PF6
(2a): Yield: 74% (99 mg), light-yellow solid. 1H NMR (500 MHz,
(CD3)2CO)): d=8.31 (dd, 1H, J=6.9, 0.6 Hz; Ar-H a), 7.67 (dd, 1H,
J=8.3, 1.2 Hz; Ar-H a), 7.47–7.41 (m, 1H; Ar-H a), 7.14 (td, 1H, J=
6.9, 1.7 Hz; Ar-H a), 6.29 (d, 1H, J=6.1 Hz; Ar-H cym), 6.19 (d, 1H,
J=6.1 Hz; Ar-H cym), 6.03 (d, 1H, J=6.1 Hz; Ar-H cym), 5.87 (d, 1H,
J=6.1 Hz; Ar-H cym), 4.50 (s, 6H; H pta), 4.28–4.11 (m, 6H; H pta),
2.71 (hept, 1H, J=7.0 Hz; Ar-CH(CH3)2 cym), 2.15 (s, 3H; Ar-CH3
cym), 1.26 ppm (dd, 6H, J=15.2, 7.0 Hz; Ar-CH(CH3)2 cym); 31P NMR
7.97 (dd, 1H, J=6.8, 0.6 Hz; Ar-H b), 6.97 (dt, 1H, J=7.1, 1.0 Hz;
Ar-H b), 6.66 (t, 1H, J=7.1 Hz; Ar-H b), 5.48 (d, 2H, J=6.0 Hz; Ar-H
cym), 5.27 (d, 2H, J=6.0 Hz; Ar-H cym), 2.82 (hept, 1H, J=7.0 Hz;
Ar-CH(CH3)2 cym), 2.41 (s, 3H; Ar-CH3 b), 2.24 (s, 3H; Ar-CH3 cym),
1.26 ppm (d, 6H, J=7.0 Hz; Ar-CH(CH3)2 cym); IR selected bands
(ATR): n˜ =3102, 2961, 2861, 1558, 1402, 1193, 1136, 1072, 777,
657 cmꢁ1; UV/Vis (l (e), c=5ꢂ10ꢁ5 m, MeOH): 276 (12260), 488 nm
(568 Lmolꢁ1 cmꢁ1); ESI-HRMS (CH3CN): m/z calcd for [MꢁCl]+:
376.0309; found: 376.0315; elemental analysis calcd (%) for
C16H20ClNORuS: C 46.77, H 4.91, N 3.41; found: C 46.45, H 4.86, N
3.30.
(202 MHz, (CD3)2CO)): d=ꢁ31.62 (P-pta), ꢁ144.25 ppm (hept, JPF
=
708 Hz; PF6); IR selected bands (ATR): n˜ =3112, 2932, 1460, 1242,
974, 947, 834, 765, 557, 481 cmꢁ1; UV/Vis (l (e), c=5ꢂ10ꢁ5 m,
MeOH): 297 (10986), 375 nm (2150 Lmolꢁ1 cmꢁ1); ESI-HRMS
(CH3CN): m/z calcd for [MꢁPF6]+: 519.0921; found: 519.0924; ele-
mental analysis calcd (%) for C21H30F6N4OP2RuS: C 38.01, H 4.56, N
8.44; found: C 37.89, H 4.43, N 8.29.
[(h6-p-Cymene)Ru(1-hydroxy-4-methylpyridine-2(1H)-thionato)Cl]
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(1c): Yield: 57% (150 mg), red solid. H NMR (500 MHz, CDCl3): d=
7.90 (d, 1H, J=6.9 Hz; Ar-H c), 7.23 (d, 1H, J=1.3 Hz; Ar-H c), 6.51
(dd, 1H, J=6.9, 1.9 Hz; Ar-H c), 5.45 (d, 2H, J=5.9 Hz; Ar-H cym),
5.25 (d, 2H, J=5.9 Hz; Ar-H cym), 2.82 (hept, 1H, J=7.0 Hz; Ar-
CH(CH3)2 cym), 2.24 (s, 3H; Ar-CH3 cym), 2.17 (s, 3H; Ar-CH3 c),
1.27 ppm (d, 6H, J=7.0 Hz; Ar-CH(CH3)2 cym); IR selected bands
(ATR): n˜ =3097, 2959, 2865, 1464, 1167, 1131, 856, 800, 775,
621 cmꢁ1; UV/Vis (l (e), c=5ꢂ10ꢁ5 m, MeOH): 283 (12962), 489 nm
(574 Lmolꢁ1 cmꢁ1); ESI-HRMS (CH3CN): m/z calcd for [MꢁCl]+:
376.0309; found: 376.0317; elemental analysis calcd (%) for
C16H20ClNORuS: C 46.77, H 4.91, N 3.41; found: C 46.73, H 4.92, N
3.45.
[(h6-p-Cymene)Ru(1-hydroxy-3-methylpyridine-2(1H)-thionato)-
pta]PF6 (2b): Yield: 83% (110 mg), light-yellow solid. 1H NMR
(500 MHz, (CD3)2CO)): d=8.20 (d, 1H, J=6.7 Hz; Ar-H b), 7.39 (d,
1H, J=7.1 Hz; Ar-H b), 7.07 (t, 1H, J=7.1 Hz; Ar-H b), 6.28 (d, 1H,
J=6.1 Hz; Ar-H cym), 6.18 (d, 1H, J=6.1 Hz; Ar-H cym), 6.03 (d, 1H,
J=6.1 Hz; Ar-H cym), 5.86 (d, 1H, J=6.1 Hz; Ar-H cym), 4.48 (s, 6H;
H pta), 4.26–4.08 (m, 6H; H pta), 2.73 (hept, 1H, J=6.9 Hz; Ar-
CH(CH3)2 cym), 2.48 (s, 3H; Ar-CH3 b), 2.17 (s, 3H; Ar-CH3 cym),
1.27 ppm (dd, 6H, J=16.2, 6.9 Hz; Ar-CH(CH3)2 cym); 31P NMR
[(h6-p-Cymene)Ru(1-hydroxy-5-methylpyridine-2(1H)-thionato)Cl]
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(1d): Yield: 52% (137 mg), red solid. H NMR (500 MHz, CDCl3): d=
(202 MHz, (CD3)2CO)): d=ꢁ31.70 (P-pta), ꢁ144.25 ppm (hept, JPF
=
7.89 (s, 1H; Ar-H d), 7.32 (d, 1H, J=8.4 Hz; Ar-H d), 6.87 (dd, 1H,
J=8.4, 1.1 Hz; Ar-H d), 5.46 (d, 2H, J=6.1 Hz; Ar-H cym), 5.25 (d,
2H, J=6.1 Hz; Ar-H cym), 2.82 (hept, 1H, J=6.9 Hz; Ar-CH(CH3)2
cym), 2.24 (s, 3H; Ar-CH3 cym), 2.14 (s, 3H; Ar-CH3 d), 1.27 ppm (d,
6H, J=6.9 Hz; Ar-CH-(CH3)2 cym); IR selected bands (ATR): n˜ =3041,
2959, 2865, 1477, 1145, 850, 814, 744, 671, 542 cmꢁ1; UV/Vis (l (e),
c=5ꢂ10ꢁ5 m, MeOH): 281 (11358), 489 nm (518 Lmolꢁ1 cmꢁ1); ESI-
HRMS (CH3CN): m/z calcd for [MꢁCl]+: 376.0309; found: 376.0315;
elemental analysis calcd (%) for C16H20ClNORuS: C 46.77, H 4.91, N
3.41; found: C 46.78, H 4.81, N 3.37.
707 Hz; PF6); IR selected bands (ATR): n˜ =3087, 2964, 2875, 1427,
1240, 972, 946, 829, 581, 556 cmꢁ1; UV/Vis (l (e), c=5ꢂ10ꢁ5 m,
MeOH): 290 (12238), 369nm (2782 Lmolꢁ1 cmꢁ1); ESI-HRMS
(CH3CN): m/z calcd for [MꢁPF6]+: 533.1078; found: 533.1078; ele-
mental analysis calcd (%) for C22H32F6N4OP2RuS: C 39.00, H 4.76, N
8.27; found: C 39.02, H 4.72, N 7.99.
[(h6-p-Cymene)Ru(1-hydroxy-4-methylpyridine-2(1H)-thionato)-
pta]PF6 (2c): Yield: 80% (106 mg), dark-orange solid. 1H NMR
(500 MHz, (CD3)2CO)): d=8.16 (d, 1H, J=6.9 Hz; Ar-H c), 7.48 (s,
1H; Ar-H c), 6.97 (dd, 1H, J=6.9, 2.1 Hz; Ar-H c), 6.26 (d, 1H, J=
6.1 Hz; Ar-H cym), 6.16 (d, 1H, J=6.1 Hz; Ar-H cym), 6.01 (d, 1H,
J=6.1 Hz; Ar-H cym), 5.85 (d, 1H, J=6.1 Hz; Ar-H cym), 4.50 (s, 6H;
H pta), 4.26–4.10 (m, 6H; H pta), 2.69 (hept, 1H, J=6.9 Hz; Ar-
CH(CH3)2 cym), 2.30 (s, 3H; Ar-CH3 c), 2.14 (s, 3H; Ar-CH3 cym),
1.25 ppm (dd, 6H, J=14.3, 6.9 Hz; Ar-CH(CH3)2 cym); 31P NMR
[(h6-p-Cymene)Ru(1-hydroxy-6-methylpyridine-2(1H)-thionato)Cl]
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(1e): Yield: 57% (149 mg), red solid. H NMR (500 MHz, CDCl3): d=
7.31 (d, 1H, J=8.1 Hz; Ar-H e), 6.91 (t, 1H, J=7.6 Hz; Ar-H e), 6.61
(dd, 1H, J=7.3, 0.7 Hz; Ar-H e), 5.50 (d, 2H, J=4.4 Hz; Ar-H cym),
5.23 (s, 2H; Ar-H cym), 2.83 (hept, 1H, J=7.0 Hz; Ar-CH(CH3)2 cym),
2.50 (s, 3H; Ar-CH3 e), 2.24 (s, 3H; Ar-CH3 cym), 1.31 ppm (d, 6H,
J=7.0 Hz; Ar-CH(CH3)2 cym); IR selected bands (ATR): n˜ =3036,
2956, 2867, 1552, 1458, 1197, 1155, 863, 776, 651 cmꢁ1; UV/Vis (l
(e), c=5ꢂ10ꢁ5 m, MeOH): 279 (9832), 483 nm (510 Lmolꢁ1 cmꢁ1);
ESI-HRMS (CH3CN): m/z calcd for [MꢁCl]+: 376.0309; found:
376.0310; elemental analysis calcd (%) for C16H20ClNORuS: C 46.77,
H 4.91, N 3.41; found: C 46.58, H 4.79, N 3.40.
(202 MHz, (CD3)2CO)): d=ꢁ31.58 (P-pta), ꢁ147.74 ppm (hept, JPF
=
708 Hz; PF6); IR selected bands (ATR): n˜ =2967, 2881, 1467, 1245,
974, 947, 832, 742, 581, 556 cmꢁ1; UV/Vis (l (e), c=5ꢂ10ꢁ5 m,
MeOH): 296 (11644), 379 nm (2062 Lmolꢁ1 cmꢁ1); ESI-HRMS (CH3CN)
m/z calcd for [MꢁPF6]+: 533.1078; found: 533.1075; elemental
analysis calcd (%) for C22H32F6N4OP2RuS: C 39.00, H 4.76, N 8.27;
found: C 38.92, H 4.74, N 8.06.
General procedure for obtaining 2a–e: A reaction mixture con-
taining the appropriate chlorido complex 1a–e (80 mg, 1 mol.
equiv.), ground phosphine ligand pta (1.5 mol. equiv.), and NH4PF6
(1.5 mol. equiv.) in dichloromethane (30 mL) was stirred in the dark
at room temperature for 48 h, during which the colour changed
from red-orange to orange. The mixture was concentrated using a
rotary evaporator and the resulting suspension was filtered
through a Celite pad to remove precipitated NH4Cl, unreacted
NH4PF6, and pta. The mother liquor was concentrated (to approxi-
mately 2 mL) to obtain an oily residue. Addition of cold diethyl
ether (10–20 mL) resulted in precipitation of the product. If
needed, an ultrasonic bath was used to aid precipitation. The sus-
pension was left to stand for 10 min at 48C, and then the product
[(h6-p-Cymene)Ru(1-hydroxy-5-methylpyridine-2(1H)-thionato)-
pta]PF6 (2d): Yield: 79% (105 mg), light-yellow solid. 1H NMR
(500 MHz, (CD3)2CO)): d=8.18 (s, 1H; Ar-H d), 7.55 (d, 1H, J=
8.3 Hz; Ar-H d), 7.33–7.29 (m, 1H; Ar-H d), 6.27 (d, 1H, J=6.1 Hz;
Ar-H cym), 6.17 (d, 1H, J=6.1 Hz; Ar-H cym), 6.02 (d, 1H, J=6.1 Hz;
Ar-H cym), 5.84 (d, 1H, J=6.1 Hz; Ar-H cym), 4.50 (s, 6H; H pta),
4.27–4.09 (m, 6H; H pta), 2.70 (hept, 1H, J=7.0 Hz; Ar-CH(CH3)2
cym), 2.27 (s, 3H; Ar-CH3 d), 2.14 (s, 3H; Ar-CH3 cym), 1.25 ppm
(dd, 6H, J=13.7, 7.0 Hz; Ar-CH(CH3)2 cym); 31P NMR (202 MHz,
(CD3)2CO)): d=ꢁ31.67 (P-pta), ꢁ144.25 ppm (hept, JPF =708 Hz;
PF6); IR selected bands (ATR): n˜ =2964, 2878, 1479, 1141, 972, 946,
833, 740, 576, 566 cmꢁ1; UV/Vis (l (e), c=5ꢂ10ꢁ5 m, MeOH): 296
(11754), 379 nm (2192 Lmolꢁ1 cmꢁ1); ESI-HRMS (CH3CN): m/z calcd
Chem. Eur. J. 2019, 25, 1 – 15
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ꢁ 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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