Inorganic Chemistry
Article
CHarom.), 7.21 (1H, d, J(HH) = 7.1 Hz, CHarom.), 7.08 and 7.05 (2H,
ppm. ESI-MS (m/z): 528.2 [M-PF6]+, 487.1 [M-MeCN-PF6]+. Anal.
Calcd for C20H25F6IrN5P (672.63): C, 35.71; H, 3.75; N, 10.41.
Found: C, 35.10 ; H, 3.30 ; N 9.90%. Despite several attemps, no
better analysis data were obtained, owing to the air- and moisture-
sensitivity of this complex.
AB spin system, CHimid.,
3J(HH) = 1.6 Hz), 7.04 (1H, overlap,
CHarom.), 6.96 (1H, d, J(HH) = 6.8 Hz, CHarom.), 6.87 (1H, s,
C···CH···C), 4.93 (2H, s, NCH2), 3.87 (3H, s, NCH3), 3.71 (2H, br,
PCH2); 13C{1H} NMR (CD3CN): δ 138.4 (s, Carom.), 136.3 (s,
Carom.), 134.1 (s, Carom.), 134.0 (s, Carom.), 132.0 (s, Carom.), 130.2 (s,
Carom.), 130.1 (s, Carom.), 130.0 (s, Carom.), 129.5 (s, Carom.), 126.9 (s,
Carom.), 123.9 (s, Cimid.), 122.8 (s, Cimid.), 55.1 (s, NCH2), 39.2 (s,
NCH3), 34.1 (s, PCH2), the resonance of the coordinated NHC
carbon could not be observed, probably because of the poor solubility
of the complex in CD3CN; 31P{1H} NMR (CD3CN): δ 12.22 (dd,
1J(P-107Ag) = 488 Hz, 1J(P-109Ag) = 555 Hz), −142.91 (sept., 1J(PF) =
711 Hz, PF6) ppm. ESI-MS (m/z): 371.2 (ligand), 477.1 [1/2(M−
2PF6)]+. Anal. Calcd for C48H46N4P4F12Ag2 (1246.52): C, 46.25; H,
3.72; N, 4.49. Found: C, 45.95; H, 3.90; N, 4.55%.
Synthesis of 1-Methyl-3-(3-hydroxyphenyl)imidazolium Io-
dide. Solid 1-(3-hydroxyphenyl)-imidazole (0.512 g, 3.20 mmol) and
iodomethane (5.0 mL) were mixed and stirred for 3 h. The suspension
was filtered. The crude solid was washed with Et2O (2 × 30 mL)
leading to a gray product. Recrystallization from MeOH/Et2O/
pentane yielded the product as a white solid (0.863 g, 2.86 mmol,
1
89%). H NMR (d6-DMSO): δ 10.23 (1H, br s, OH), 9.72 (1H, br s,
NCHN), 8.25 (1H, br s, CHimid.), 7.95 (1H, br s, CHimid.), 7.44 (1H, t,
2
3J(HH) = 6.7 Hz, CHarom.), 7.18 (1H, d, J(HH) = 6.7 Hz, CHarom.),
2
7.11 (1H, s, CHarom.), 6.98 (1H, d, J(HH) = 6.7 Hz, CH CHarom.),
3.95 (3H, s, NCH3); 13C{1H} NMR (d6-DMSO): δ 159.2 (C−OH),
136.3 (Carom.), 136.2 (NCN), 131.6 (Carom.), 124.9 (Cimid.), 121.4
(Cimid.), 117.1 (Carom.), 112.6 (Carom.), 109.3 (Carom.), 36.7 (NCH3)
ppm. ESI-MS (m/z): 175.1 [M-I]+. Anal. Calcd for C10H11IN2O
(302.11): C, 39.76; H, 3.67; N, 9.27. Found: C, 39.73; H, 3.81; N,
9.06%.
Synthesis of [Ir(cod)(μ-P-NHC,κP,κCNHC)]2(PF6)2 (4). Solid 2·PF6
(0.103 g, 0.200 mmol), [Ir(cod)(μ-Cl)]2 (0.067 g, 0.10 mmol), and
Cs2CO3 (0.098 g, 0.30 mmol) were mixed and heated in acetonitrile
(15 mL) at 60 °C for 3 h. The suspension was then allowed to cool to
room temperature and the solvent was removed under reduced
pressure. The orange solid was dissolved in CH2Cl2 (10 mL), and the
solution was filtered, concentrated to 5 mL, and diethyl ether was
added to precipitate an orange solid. (0.13 g, 0.080 mol, 80%). Single
crystals of 4·2THF suitable for X-ray diffraction studies were obtained
by slow diffusion of THF into a saturated CH2Cl2 solution of the
Synthesis of 1-Methyl-3-(3-(di-tert-butylphosphinooxy)-
phenyl)imidazolium Iodide (8a). 1-Methyl-3-(3-hydroxyphenyl)
imidazolium iodide (0.863 g, 2.86 mmol) and excess NEt3 (1.00 mL,
7.17 mmol) were mixed in THF (50 mL). Di-tert-butyl-chlorophos-
phine (0.584 mL, 3.00 mmol) was added via a syringe and the reaction
mixture was stirred at room temperature for 15 h. The resulting
suspension was filtered, and the solvent was removed in vacuo. The
crude solid was recrystallized from THF/Et2O, yielding the pure
product as a white solid. (0.597 g, 1.34 mmol, 47%). 1H NMR
1
complex. H NMR (CD3CN): δ 7.51−7.48 (3H, m, CHarom.), 7.40−
7.32 (6H, m, CHarom.), 7.25 (1H, d, 3J(HH) = 2.0 Hz, CHimid.), 7.19−
3
7.11 (4H, m, CHarom.), 6.78 (1H, d, J(HH) = 2.0 Hz, CHimid.), 5.94
(1H, br s, C···CH···C), 5.80 (1H, A part of an AB spin system,
simulated, 2J(HH) = 14.9 Hz, NCHH), 5.03 (1H, B part of an AB spin
4
2
(CDCl3): δ 10.60 (pseudo t, J(HH) = 1.5 Hz, 1H, NCHN), 7.64
system, simulated, J(HH) = 14.9 Hz, NCHH), 4.51 (4H, m, cod),
3
4
(pseudo t, J(HH) = J(HH) = 1.7 Hz, 1H, CHimid.), 7.61 (pseudo t,
4.07 (3H, s, N−CH3), 3.87 (2H, m, cod), 3.68 (2H, m, cod), 3.56
(1H, A part of an AB spin system, simulated, 2J(HH) = 7.7 Hz,
PCHH), 3.51 (2H, B part of an AB spin system, simulated, 2J(HH) =
7.7 Hz, PCHH), 3.10 (2H, m, cod), the other cod protons are partly
masked by the solvent; 13C{1H} NMR (CD3CN): δ 175.1 (NCN),
136.4 (d, J(PC) = 12.2 Hz, Carom.), 135.8 (s, Carom.), 133.6 (d, J(PC) =
10.0 Hz, Carom.), 132.9 (s, Carom.), 131.9 (s, Carom.), 130.9 (d, J(PC) =
3.8 Hz, Carom.), 130.0 (d, J(PC) = 4.2 Hz, Carom.), 129.8 (s, Carom.),
129.7 (s, Carom.), 129.6 (s, Carom.), 125.3 (s, Cimid.), 122.9 (s, Cimid.),
88.8 (d, J = 11.8 Hz, cod), 87.3 (d, J = 11.8 Hz, cod), 82.3 (s, cod),
79.0 (s, cod), 55.0 (s, NCH2), 38.6 (s, NCH3), 37.1 (d, J(PC) = 26.2
Hz, PCH2), 33.2 (d, J(PC) = 41.6 Hz, cod), 29.4 (d, J(PC) = 48.0 Hz,
cod); 31P{1H} NMR (CD3CN): δ 16.88 (s, PPh2), −143.44 (sept,
1J(PF) = 706 Hz, PF6) ppm. ESI-MS (m/z): 671.2 [M−2(PF6)]2+.
Anal. Calcd for (C32H35F6IrN2P2)2 (1631.58): C, 47.11; H, 4.32; N,
3.43. Found: C, 46.82; H, 4.28; N, 3.33%.
4
3J(HH) = J(HH) = 1.7 Hz, 1H, CHimid.), 7.44−7.51 (m, 2H), 7.39−
3
7.43 (m, 2H), 4.29 (s, 3H, NCH3), 1.20 [d, J(PH) = 12.0 Hz, 18H,
CH3, P(t-Bu)2]; 13C{1H} NMR (CDCl3): δ 161.3 (d, J(PC) = 4.9
2
Hz, C−O), 136.1 (Carom.), 135.3 (NCN), 131.5 (Carom.), 124.3 (Cimid.),
3
120.7 (Cim3 id.), 120.2 (d, J(PC) = 11.8 Hz, Carom.), 115.0 (Carom.),
1
111.8 (d, J(PC) = 11.2 Hz, Carom.), 37.4 (NCH3), 35.7 [d, J(PC) =
2
25.0 Hz, Cquart., 2 × P(t-Bu)2], 27.1 [d, J(PC) = 15.4 Hz, CH3, 2 ×
P(t-Bu)2]; 31P{1H} NMR (CDCl3): δ 159.92 ppm. ESI-MS (m/z):
319.2 [M-I]+. Anal. Calcd for C18H28IN2OP (446.31): C, 48.44; H,
6.32; N, 6.28. Found: C, 48.17; H, 6.29; N, 6.07%.
Synthesis of the Tetranuclear Silver Cluster [Ag2(μ3-I)2(μ-OP-
NHC,κP,κCNHC)]2 (9a). In a Schlenk tube, Ag2O (0.023 g, 0.10 mmol)
and AgI (0.047 g, 0.20 mmol) were added to a solution of 1-methyl-3-
(3-(di-tert-butylphosphinooxy)phenyl)imidazolium iodide (0.089 g,
0.20 mmol) in CH2Cl2 (15 mL). The mixture was stirred at room
temperature for 15 h. The solvent was removed in vacuo, and the solid
obtained was recrystallized from CH2Cl2/Et2O, yielding the product as
a colorless solid (0.16 g, 0.087 mmol, 87%). Single crystals of
9a·CH2Cl2 suitable for X-ray diffraction studies were obtained by slow
diffusion of Et2O into a saturated dichloromethane solution of the
Synthesis of [IrH(CNHCCCNHC)(MeCN)]PF6 (7). Solid 1,1′-((4,6-
dimethyl-1,3-phenylene)bis(methylene)) bis (3-methyl-1H-imidazol-
3-ium) dihexafluorophosphate (5) (0.231 g, 0.394 mmol), [Ir-
(coe)2(μ-Cl)]2 (0.180 g, 0.200 mmol) and Cs2CO3 (0.326 g, 1.00
mmol) were mixed and heated in a stirred solution of acetonitrile (35
mL) and THF (15 mL) at 85 °C for 3 h. The suspension was then
allowed to cool to room temperature and the solution was filtered. The
filtrate was concentrated to 5 mL and ether was added to precipitate a
pale yellow solid. (0.201 g crude, 0.299 mmol, 75.8% yield based on
1
complex. H NMR (CD2Cl2): δ 7.55 (br s, 1H, CHarom.), 7.38 (t,
3J(HH) = 8.0 Hz, 1H, CHarom.), 7.20 (d, 3J(HH) = 1.8 Hz, 1H,
3
CHimid.), 7.11−7.16 (m, 2H, CHarom.), 7.10 (d, J(HH) = 1.8 Hz, 1H,
3
CHimid.), 3.97 (s, 3H, NCH3), 1.41 [d, J(PH) = 14.6 Hz, 18H, P(t-
Bu)2]; 13C{1H} NMR (CD2Cl2): δ 158.6 (C−O), 142.1 (C−N),
130.2 (Carom.), 122.3 (Cimid.), 121.7 (Cimid.), 121.1 (d, 3J(PC) = 2.7 Hz,
Carom.), 119.4 (Car1om.), 118.0 (d, 3J(PC) = 8.1 Hz, Carom.), 39.5
(NCH3), 39.2 [d, J(PC) = 0.8 Hz, Cquart., 2 × P(t-Bu)2], 28.2 [d,
2J(PC) = 10.0 Hz, CH3, 2 × P(t-Bu)2], the resonance of the
coordinated NHC carbon could not be observed, probably because of
the poor solubility of the complex in CD2Cl2; 31P{1H} NMR
1
3
Ir). H NMR (CD3CN): δ 7.27 (1H, d, J(HH) = 1.9 Hz, CHimid.),
7.26 (1H, d, 3J(HH) = 1.9 Hz, CHimid.), 7.07 (1H, d, 3J(HH) = 1.9 Hz,
CHimid.), 7.01 (1H, d, 3J(HH) = 1.9 Hz, CHimid.), 6.47 (1H, s,
2
CHarom.), 5.19 (2H, m, A part of an AB spin system, J(HH) = 13.9
Hz, CHH), 5.16 (2H, m, a part of an AB spin system, J(HH) = 15.0
2
Hz, CHH), 5.06 (2H, m, b part of an AB spin system, 2J(HH) = 15.0
Hz, CHH), 4.38 (2H, m, B part of an AB spin system, 2J(HH) = 13.9
Hz, CHH), 3.88 (3H, s, N−CH3), 3.67 (3H, s, N−CH3), 2.30 (3H, s,
C−CH3), 2.27 (3H, s, C−CH3), −22.07 (1H, s, Ir−H); 13C{1H}
NMR (CD3CN): δ 164.5 (NCN), 164.1 (NCN), 139.0 (Carom.), 138.7
(Carom.), 135.0 (Carom.), 132.5 (Carom.), 131.9 (Carom.), 127.2 (Carom.),
122.4 (Cimid.), 122.0 (Cimid.), 121.9 (Cimid.), 121.4 (Cimid.), 56.1 (CH2),
53.4 (CH2), 38.2 (NCH3), 37.2 (NCH3), 20.6 (CH3), 20.5 (CH3);
1
(CD2Cl2): δ 158.33 (br, J(P−Ag) not resolved) ppm. ESI-MS (m/
z): 1576.6 [M+H]+, 1468.7 [M+2H−Ag]+, 1340.8 [M+H−AgI]+,
1234.9 [M-AgI2]+. Anal. Calcd for C36H54Ag4I4N4O2P2·3CH2Cl2
(1830.68): C, 25.59; H, 3.30; N, 3.06. Found: C, 25.14; H, 3.26; N,
3.15%.
Synthesis of [IrH(I)(PO-NHC,κP,κC,κCNHC)
Me] (10a). Solid 8a
1
31P{1H} NMR (CD3CN): δ −144.71 (sept., J(PF) = 709 Hz, PF6)
(0.178 g, 0.399 mmol), [Ir(coe)2(μ-Cl)]2 (0.180 g, 0.200 mmol), and
I
dx.doi.org/10.1021/ic302854t | Inorg. Chem. XXXX, XXX, XXX−XXX