2-Vinylpyridine Iridium Complexes
Organometallics, Vol. 23, No. 8, 2004 1915
133.35 (s, IrCHdCH), 138.21, 147.9 (both s, CH), 151.69 (d,
J CP ) 7.8, IrCHdCH), 165.93 (s, C).
19.38, 19.44 (both s, PCHCH3), 24.34 (d, J CP ) 29.4, PCHCH3),
119.65 (s, CH), 120.41 (d, J CP ) 2.8, CH), 122.61 (s, IrC(Ph)d
CH2), 124.36, 126.60, 127.12 (all s, CH), 133.24 (d, J CP ) 7.8,
IrC(Ph)dCH2), 133.62, 139.01, 148.15 (all s, CH), 153.34 (s,
C), 155.27 (d, J CP ) 6.9, IrCHdCH), 166.18 (s, C).
P r ep a r a t ion of [Ir (E t ){NC5H 4-2-Z-(CH dCH )-K-N,C}-
(NCCH3)2(P iP r 3)]BF 4 (7). A solution of 3 (150 mg, 0.24 mmol)
in CH2Cl2 (8 mL) was stirred under ethylene atmosphere (P
) 1.1 bar) during 2 h at room temperature. The resulting
orange solution was concentrated to ca. 0.5 mL and diethyl
ether was slowly added to give a pale yellow solid. The solid
was separated by decantation, washed with diethyl ether, and
dried in vacuo: yield 118 mg (75%). Anal. Calcd for C22H38N3-
BF4IrP: C, 40.37, H, 5.85; N, 6.42. Found: C, 40.19; H, 5.58;
N, 6.03. ΛM(acetone) ) 104 Ω-1 cm2 mol-1 (1:1). 1H NMR
(CDCl3, 293 K) δ 0.27 (t, J HH ) 7.5, 3H, IrCH2CH3), 0.62 (dqd,
P r ep a r a t ion of [Ir (E-CH dCH tBu ){NC5H 4-2-Z-(CH d
CH)-K-N,C}(NCCH3)2(P iP r 3)]BF 4 (10). The procedure de-
scribed for 9 with use of tBuCtCH (35 µL, 0.29 mmol) as the
substrate produced a pale yellow solid: yield 128 mg (75%).
Anal. Calcd for C26H44N3BF4IrP: C, 44.07; H, 6.26; N, 5.93.
Found: C, 43.75; H, 5.96; N, 5.73. MS (FAB+, m/z (%)) 622
(8) [M+]. ΛM(acetone) ) 99 Ω-1 cm2 mol-1 (1:1). 1H NMR
(CDCl3, 293 K) δ 0.61 (s, 9H, C(CH3)3), 1.23 (dd, J HP ) 13.7,
J HH ) 7.2, 9H, PCHCH3), 1.25 (dd, J HP ) 13.2, J HH ) 7.2, 9H,
PCHCH3), 2.19 (br, 3H, NCCH3), 2.57 (m, 3H, PCHCH3), 2.67
(s, 3H, NCCH3), 4.86 (dd, J HH ) 16.0, J HP ) 0.5, 1H, IrCHd
CHtBu), 5.80 (dd, J HH ) 16.0, J HP ) 2.7, 1H, IrCHdCHtBu),
6.89 (d, J HH ) 8.3, 1H, IrCHdCH), 7.15 (t, J HH ) 6.6, 1H, CH),
7.21 (d, J HH ) 7.8, 1H, CH), 7.60 (t, J HH ) 7.8, 1H, CH), 8.55
(m, 2H, IrCHdCH + CH). 31P{1H} NMR (CDCl3, 293 K) δ 1.80
(s). 13C{1H} NMR (CDCl3, 293 K) δ 3.13 (br, NCCH3) 3.92 (s,
NCCH3), 18.92 (d, J CP ) 2.3, PCHCH3), 19.50 (s, PCHCH3),
23.76 (d, J CP ) 30.0, PCHCH3), 29.82 (s, C(CH3)3), 34.54 (s,
C(CH3)3), 102.80 (d, J CP ) 9.1, IrCHdCHtBu), 119.40 (d, J CP
) 2.3, CH), 120.50 (s, CH), 120.55 (s, NCCH3), 121.01 (br,
NCCH3), 133.76 (d, J CP ) 3.0, IrCHdCH), 138.39 (s, CH),
143.38 (s, IrCHdCHtBu), 147.35 (s, CH), 155.69 (d, J CP ) 8.3,
IrCHdCH), 165.79 (d, J CP ) 2.3, C).
J HH ) 10.8, 7.5, J HP ) 1.8, 1H, IrCH2CH3), 1.27 (dd, J HP
)
12.9, J HH ) 7.2, 18H, PCHCH3), 1.27 (m, 1H, IrCH2CH3), 2.12
(br, 3H, NCCH3), 2.55 (m, 3H, PCHCH3), 2.60 (br, 3H, NCCH3),
6.87 (d, J HH ) 8.4, 1H, IrCHdCH), 7.21 (m, 2H, CH), 7.64 (t,
J HH ) 7.5, 1H, CH), 8.70 (dd, J HH ) 8.4, J HP ) 4.5, 1H, IrCHd
CH), 8.75 (m, 1H, CH). 31P{1H} NMR (CDCl3, 293 K) δ -0.04
(s). 13C{1H} NMR (CDCl3, 293 K) δ -15.66 (d, J CP ) 5.6, IrCH2-
CH3), 2.82, 3.73 (both br, NCCH3), 15.57 (s, IrCH2CH3), 19.07,
19.28 (both s, PCHCH3), 23.56 (d, J CP ) 29.5, PCHCH3), 119.31
(s, CH), 120.41 (d, J CP ) 3.2, CH), 121.60, 122.99 (both br,
NCCH3), 133.24 (d, J CP ) 2.7, IrCHdCH), 138.56, 148.14 (both
s, CH), 157.48 (d, J CP ) 7.8, IrCHdCH), 166.18 (d, J CP ) 1.9,
C).
P r ep a r a tion of [Ir (CHdCH2){NC5H4-2-Z-(CHdCH)-K-
N,C}(NCCH3)2(P iP r 3)]BF 4 (8). A slow acetylene stream was
passed during ca. 3 min through a solution of 3 (150 mg, 0.24
mmol) in CH2Cl2 (8 mL) at room temperature. The resulting
pale orange solution was concentrated to ca. 0.5 mL and
diethyl ether was slowly added to give a white solid. The solid
was separated by decantation, washed with diethyl ether, and
dried in vacuo: yield 124 mg (80%). Anal. Calcd for C22H36N3-
BF4IrP: C, 40.49; H, 5.56; N, 6.44. Found: C, 40.83; H, 5.67;
N, 6.56. MS (FAB+, m/z (%)) 484 (100) [M+ - 2 NCCH3)]. ΛM-
P r ep a r a tion of [Ir {Z-C(P h )dCHP h }{NC5H4-2-Z-(CHd
CH)-K-N,C}(NCCH3)2(P iP r 3)]BF 4 (11). The procedure de-
scribed for 9 with PhCtCPh (51.2 mg, 0.29 mmol) as the
substrate produced a yellow solid: yield 164 mg (85%). Anal.
Calcd for C34H44N3BF4IrP: C, 50.75; H, 5.51; N, 5.22. Found:
C, 50.49; H, 5.59; N, 5.30. MS (FAB+, m/z (%)) 636 (55) [M+
-
2 NCCH3]. ΛM(acetone) ) 109 Ω-1 cm2 mol-1 (1:1). 1H NMR
(CDCl3, 293 K) δ 1.43, 1.46 (both dd, J HP ) 13.5, J HH ) 6.9,
9H each, PCHCH3), 2.25, 2.29 (both br, 3H each, NCCH3), 2.88
(m, 3H, PCHCH3), 6.15 (s, 1H, IrC(Ph)dCHPh), 6.47 (dd, J HH
) 6.9, 2.2, 2H, CH), 7.00 (d, J HH ) 8.1, 1H, IrCHdCH), 7.01-
7.08 (all m, 9H, CH), 7.23 (t, J HH ) 6.6, 1H, CH), 7.26 (d, J HH
) 7.4, 1H, CH), 7.69 (t, J HH ) 7.7, 1H, CH), 8.42 (m, 1H, CH),
8.99 (dd, J HH ) 8.1, J HP ) 4.5, 1H, IrCHdCH). 31P{1H} NMR
(CDCl3, 293 K) δ -3.96 (s). 13C{1H} NMR (CDCl3, 293 K) δ
2.99, 3.18 (both br, NCCH3), 19.62 (d, J CP ) 1.6, PCHCH3),
19.66 (d, J CP ) 2.0, PCHCH3), 24.59 (d, J CP ) 29.1, PCHCH3),
119.54 (d, J CP ) 1.6, CH), 120.56 (d, J CP ) 3.2, CH), 121.12,
121.40 (both br, NCCH3), 124.42, 124.66, 127.44, 128.01 (all
1
(acetone) ) 119 Ω-1 cm2 mol-1 (1:1). H NMR (CDCl3, 293 K)
δ 1.25, 1.27 (both dd, J HP ) 13.4, J HH ) 6.6, 9H each, PCHCH3),
2.19 (br, 3H, NCCH3), 2.50 (m, 3H, PCHCH3), 2.66 (s, 3H,
NCCH3), 4.69 (dd, J HH ) 17.4, 2.1, 1H, IrCHdCH2), 5.04 (dd,
J HH ) 10.2, 2.1, 1H, IrCHdCH2), 6.68 (ddd, J HH ) 17.4, 10.2,
J HP ) 3.0, 1H, IrCHdCH2), 6.90 (d, J HH ) 8.4, 1H, IrCHd
CH), 7.19 (t, J HH ) 6.9, 1H, CH), 7.24 (d, J HH ) 7.8, 1H, CH),
7.63 (dd, J HH ) 7.8, 1H, CH), 8.59 (dd, J HH ) 8.4, J HP ) 4.5,
1H, IrCHdCH), 8.64 (m, 1H, CH). 31P{1H} NMR (CDCl3, 293
K) δ 1.84 (s). 13C{1H} NMR (CDCl3, 293 K) δ 3.74 (br, NCCH3)
3.93 (s, NCCH3), 18.76 (d, J CP ) 2.1, PCHCH3), 19.30 (s,
PCHCH3), 23.63 (d, J CP ) 30.0, PCHCH3), 117.77 (s, NCCH3),
117.83 (br, NCCH3), 119.66, 120.89 (both s, CH), 121.38 (s,
IrCHdCH2), 122.35 (d, J CP ) 8.0, IrCHdCH2), 134.06 (d, J CP
) 3.4, IrCHdCH), 138.74, 147.59 (both s, CH), 155.52 (d, J CP
) 8.4, IrCHdCH), 165.84 (d, J CP ) 1.8, C).
s, CH), 128.42 (d, J CP ) 7.4, IrC(Ph)dCHPh), 133.55 (d, J CP
2.9, IrC(Ph)dCHPh), 136.37 (s, IrCHdCH), 139.09 (s, CH),
139.90 (s, C), 148.45 (s, CH), 150.11 (br, C), 155.25 (d, J CP
)
)
6.3, IrCHdCH), 166.21 (d, J CP ) 1.1 C). The crystals used in
the X-ray structural determination were obtained by slow
diffusion of diethyl ether into a saturated solution of 11 in CH2-
Cl2 at 253 K.
P r ep a r a tion of [Ir {C(P h )dCH2}{NC5H4-2-Z-(CHdCH)-
K-N,C}(NCCH3)2(P iP r 3)]BF 4 (9). A solution of 3 (150 mg, 0.24
mmol) in CH2Cl2 (8 mL) was treated with PhCtCH (32 µL,
0.29 mmol) and allowed to react for 1 h at room temperature.
The resulting red solution was concentrated to ca. 0.5 mL and
diethyl ether was added to give a yellow solid. The solid was
separated by decantation, washed with diethyl ether, and dried
in vacuo: yield 146 mg (84%). Anal. Calcd for C28H40N3BF4-
IrP: C, 46.16; H, 5.53; N, 5.77. Found: C, 46.39; H, 5.67; N,
5.53. MS (FAB+, m/z (%)) 560 (30) [M+ - 2 NCCH3]. ΛM-
P r ep a r a tion of [Ir {NC5H4-2-Z-(CHdCH)-K-N,C}{NC5H4-
2-Z-(CHdCH)CH(P h )CH2-K-N,C}(NCCH3)(P iP r 3)]BF4 (12).
A solution of 9 (175 mg, 0.24 mmol) in CH2Cl2 (8 mL) was
treated with 2-vinylpyridine (31 µL, 0.29 mmol) and allowed
to react for 1 h at room temperature. The resulting orange
solution was concentrated to ca. 0.5 mL and diethyl ether was
slowly added to give a white solid. The solid was separated by
decantation, washed with diethyl ether, and dried in vacuo:
1
(acetone) ) 109 Ω-1 cm2 mol-1 (1:1). H NMR (CDCl3, 293 K)
yield 143 mg (75%). MS (FAB+, m/z (%)) 665 (15) [M+
-
δ 1.32 (dd, J HP ) 12.9, J HH ) 7.5, 9H, PCHCH3), 1.33 (dd, J HP
) 13.4, J HH ) 7.2, 9H, PCHCH3), 2.21 (s, 6H, NCCH3), 2.75
(m, 3H, PCHCH3), 4.75, 5.01 (both d, J HH ) 2.7, 1H each, IrC-
NCCH3]. ΛM(acetone) ) 112 Ω-1 cm2 mol-1 (1:1). The NMR
spectra of the CDCl3 solutions obtained from this solid revealed
the presence of compound 12 together with a mixture of
various minor additional compounds, the relative proportion
of which was different in the various preparations attempted
(between 10% and 20%). Data for 12: 1H NMR (CDCl3, 293
K) δ 1.09, 1.16 (both dd, J HP ) 12.9, J HH ) 7.2, 9H each,
PCHCH3), 2.19 (m, 3H, PCHCH3), 2.66 (s, 3H, NCCH3), 2.71
(Ph)dCH2), 6.51 (dd, J HH ) 7.2, 2.2, 2H, CH), 6.88 (d, J HH
)
8.1, 1H, IrCHdCH), 6.99 (m, 3H, CH), 7.22 (m, 3H, CH), 7.64
(t, J HH ) 7.8, 1H, CH), 8.45 (m, 1H, CH), 8.87 (dd, J HH ) 8.1,
J HP ) 4.5 1H, IrCHdCH). 31P{1H} NMR (CDCl3, 293 K) δ
-3.26 (s). 13C{1H} NMR (CDCl3, 293 K) δ 3.0 (br, NCCH3),