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Dalton Transactions
Page 8 of 10
DOI: 10.1039/C5DT02513C
Journal Name
ARTICLE
45
The ligands KN(R2PS)2 (R = Ph,42 Pri,43 But, 44) and NaLOEt
[Ru2(μ-N){N(R2PS)2}4Cl] (R = Ph (6), Pri (7)). To a solution of
and the nitrido complexes [Bun4N][Ru(N)Cl4]46 and mer- [Bun4N][Ru(N)Cl4] (50 mg, 0.1 mmol) in thf (10 mL) was added 2
[Ru(N)Cl3(AsPh3)2]24 were prepared according to literature equivalents of KN(R2PS)2 (97 mg for 6, 70 mg for 7, 0.2 mmol) in thf
methods.
(10 mL) dropwise at -78 oC. The purple solution was warmed to
room temperature and stirred for overnight. The solvent was
removed in vacuo and the residue was extracted with thf (for 6) or
Et2O (for 7). Recrystallisation from thf/hexanes (for 6) or
Et2O/hexanes (for 7) afforded a green crystalline solid.
Syntheses
mer-[Ru(NS)Cl3(AsPh3)2] (1). A mixture of mer-[Ru(N)Cl3(AsPh3)2]
(83 mg, 0.1 mmol) and elemental sulfur (3.2 mg, 0.1 mmol) in thf (5
mL) was refluxed for 2 h. The orange solid was collected and
washed with Et2O. Recrystallisation in CH2Cl2/Et2O afforded orange
blocks which were suitable for the X-ray diffraction study. Yield: 78
mg (90 %). 1H NMR (CDCl3): δ 7.76-8.03 (m, 30H, Ph). IR (KBr, cm-1):
1310 [ν(N-S)]. Anal. Calcd for C36H30As2Cl3NRuS: C, 49.93; H, 3.49, N,
1.62. Found: C, 49.50; H, 3.37; N, 1.63.
6: Yield: 90 mg (45 %). 1H NMR (CDCl3): δ 6.71-6.75 (m, 12H, Ph),
6.88-6.92 (m, 16H, Ph), 6.98-7.14 (m, 20H, Ph), 7.56-7.70 (m, 16H,
Ph), 7.74-7.81 (m, 16H, Ph), 7.83-7.87 (m, 4H, Ph). 31P {1H} NMR
(CDCl3): δ 38.6 (s), 43.6 (s). IR (KBr, cm-1): 1026 [νas(RuNRu)]. Anal.
Calcd for C96H80ClN5P8Ru2S8: C, 56.37; H, 3.94, N, 3.42. Found: C,
56.65; H, 3.91; N, 3.40.
1
7: Yield: 35 mg (23 %). H NMR (benzene-d6): δ 1.12-1.26 (m, 24H,
(CH3)2CH), 1.35-1.58 (m, 72H, (CH3)2CH), 1.85 (m, 4H, (CH3)2CH),
2.33 (m, 4H, (CH3)2CH), 2.95 (m, 4H, (CH3)2CH), 3.26 (m, 4H,
(CH3)2CH). 31P {1H} NMR (benzene-d6): δ 62.5 (s), 62.6 (s). IR (KBr,
cm-1): 1024 [νas(RuNRu)]. Anal. Calcd for C48H112ClN5P8Ru2S8: C,
38.40; H, 7.52, N, 4.66. Found: C, 38.65; H, 7.73; N, 4.88. E1/2: -0.91,
0.79 V (quasi-reversible).
mer-[Ru(NSe)Cl3(AsPh3)2] (2). A mixture of mer-[Ru(N)Cl3(AsPh3)2]
(83 mg, 0.1 mmol) and selenium (7.9 mg, 0.1 mmol) in thf (5 mL)
was refluxed overnight. The orange solid was collected and washed
with Et2O. Recrystallisation in CH2Cl2/Et2O afforded orange blocks
which were suitable for the X-ray diffraction study. Yield: 75 mg
(82%). 1H NMR (CDCl3): δ 7.33-7.88 (m, 30H, Ph). IR (KBr, cm-1):
1137 [ν(N-Se)]. Anal. Calcd for C36H30As2Cl3NRuSe·CH2Cl2: C, 44.54;
H, 3.23, N, 1.40. Found: C, 44.75; H, 3.22; N, 1.50.
trans-[Ru(NS){N(R2PS)2}2Cl] (R = Ph (3), Pri (4)). A mixture of 1 (86
mg, 0.1 mmol) and 2 equivalents of KN(R2PS)2 (97 mg for 3, 70 mg
for 4, , 0.2 mmol) in thf (5 mL) was refluxed for 2 hr. The solvent
was removed in vacuo the residue was extracted with CH2Cl2 (5 ml).
Recrystallisation from CH2Cl2/hexanes (5 mL, v:v = 1:2) afforded
orange crystals.
3: Yield: 82 mg (76 %). 1H NMR (CDCl3): δ 7.21-7.25 (m, 8H, Ph),
7.31-7.40 (m, 16H, Ph), 7.74-7.79 (m, 8H, Ph), 8.00-8.06 (m, 8H, Ph).
31P {1H} NMR (CDCl3): δ 37.8 (s). IR (KBr, cm-1): 1281 [ν(NS)]. Anal.
Calcd for C48H40ClN3P4RuS5: C, 53.40; H, 3.73, N, 3.89. Found: C,
53.10; H, 3.82; N, 3.56.
4: Yield: 59 mg (73 %). 1H NMR (CDCl3): δ 1.12-1.64 (m, 48H,
(CH3)2CH), 1.93-2.13 (m, 4H, (CH3)2CH), 2.40-2.69 (m, 4H, (CH3)2CH).
31P {1H} NMR (CDCl3): δ 63.2 (s). IR (KBr, cm-1): 1304 [ν(NS)]. Anal.
Calcd for C24H56ClN3P4RuS5: C, 35.70; H, 6.99, N, 5.20. Found: C,
35.96; H, 6.93; N, 5.34.
[Ru(NSe)LOEtCl2] (9). A mixture of 2 (90 mg, 0.1 mmol) and 1
equivalent of NaLOEt (55 mg, 0.1 mmol) in thf (5 mL) was refluxed
for 2 h, during which a yellow solution was formed. Solvent was
pumped off and the residue was extracted with CH2Cl2.
Recrystallisation from CH2Cl2/hexanes afforded yellowish brown
crystals. Yield: 48 mg (60%). 1H NMR (CDCl3): δ 1.28-1.37 (m, 18H,
CH3), 4.16-4.23 (m, 12H, CH2), 5.07 (s, 5H, Cp). 31P {1H} NMR (CDCl3):
δ 119.3-120.6 (m). Yield: Anal. Calcd for C17H35Cl2CoNO9P3RuSe: C,
25.51; H, 4.41, N, 1.75. Found: C, 25.34; H, 4.11; N, 1.83.
[Ru2(μ-N){N(But2PS)2}4] (10). To a solution of 5 (50 mg, 0.054 mmol)
in thf (10 mL) was added 1 equivalent of [Ni(cod)2] (15 mg, 0.054
o
mmol) at 0 C, during which the orange solution turned brown. The
solvent was pumped off and the residue was extracted with
thf/hexanes (5 mL, 1:1, v/v). Concentration and cooling at -20 oC
afforded dark brown crystals. Yield: 20 mg, 43%. ꢀeff (Evans method,
CDCl3) = 1.58 ꢀB. IR (KBr, cm-1): 1018 [νas(RuNRu)]. Anal. Calcd for
C64H144N5P8Ru2S8·1.5C6H12: C, 48.27; H, 8.99, N, 3.86. Found: C,
47.78; H, 9.35; N, 3.51.
[Ru2(μ-N){N(But2PS)2}4](PF6) ([10]PF6). To a solution of 10 (30 mg,
0.019 mmol) in thf (10 mL) was added 1 equivalent of ferrocenium
hexafluorophosphate (6 mg, 0.019 mmol) during which the brown
solution turned red. The red solution was stirred at room
temperature for 2 h. The solvent was pumped off and the residue
was washed with Et2O and then extracted with CH2Cl2.
Recrystallisation from CH2Cl2/Et2O/hexanes afforded red crystals.
Yield: 27 mg, 83%. 1H NMR (CDCl3): δ 1.24 (d, J = 15.2 Hz, 36H, CH3),
1.57 (d, J = 15.6 Hz, 36H, CH3). 31P {1H} NMR (CDCl3): δ 68.95 (br. s), -
trans-[Ru(NS){N(But2PS)2}2Cl] (5). Method A: A mixture of 1 (86 mg,
0.1 mmol) and 2 equivalents of KN(But2PS)2 (81 mg, 0.2 mmol) in thf
(10 mL) was stirred at room temperature for overnight. The solvent
was removed in vacuo the residue was extracted with CH2Cl2.
Recrystallisation from CH2Cl2/hexanes gave red crystalline solid.
1
Yield: 63 mg (68 %). H NMR (CDCl3): δ 1.22-1.27 (d, J = 8 Hz, 36H,
CH3), 1.54-1.60 (d, J = 8 Hz, 36H, CH3). 31P {1H} NMR (CDCl3): δ 68.8
(s). IR (KBr, cm-1): 1305 [ν(NS)]. Anal. Calcd for
C32H72ClN3P4RuS5·0.5CH2Cl2·0.5C6H14
: C, 42.42; H, 8.0; N, 4.18.
-
144.49 (sept, J = 712 Hz, PF6 ). 19F {1H} NMR (CDCl3): δ -74.65 (d, J =
Found: C, 42.48; H, 8.40; N, 3.93.
713 Hz). IR (KBr, cm-1): 1014 [νas(RuNRu)]. Anal. Calcd for
C64H144F6N5P9Ru2S8: C, 41.88; H, 7.91, N, 3.82. Found: C, 41.65; H,
7.90; N, 3.72. E1/2: -0.80, 0.80 V (irreversible).
Method B: To a solution of [Bun4N][Ru(N)Cl4] (50 mg, 0.1 mmol) in
thf (5 mL) was added 3 equivalents of KN(But2PS)2 (81 mg, 0.2
mmol) and the mixture was stirred at room temperature for
overnight. The solvent was removed in vacuo and the residue was
extracted with CH2Cl2. Recrystallisation from CH2Cl2/hexanes gave
red crystals. Yield: 23 mg (25 %).
Reaction of 3 with PPh3. To a solution of 3 (20 mg, 0.019 mmol) in
CH2Cl2 (0.5 mL) was added 1 equivalent of PPh3 (4.9 mg, 0.019
mmol). The resulting brown solution was stirred at room
temperature for 6 h. 31P {1H} NMR spectroscopy indicated that the
reaction mixture contained 6 (δ 38.6 and 43.6 ppm), SPPh3 (δ 43.2
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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Ng, Ho-Yuen
