4018
C.-Y. Wang et al. / Journal of Organometallic Chemistry 691 (2006) 4012–4020
resulting solution was filtrated through Celite followed by
concentration and crystallization from CH2Cl2/hexane to
afford yellow crystalline solids (635 mg, 99%): H NMR
7.6 Hz), 7.18 (d, 1H, J = 7.6 Hz), 7.16 (s, 1H), 7.12 (s,
1H), 6.91 (s, 2H), 6.89 (s, 1H), 6.75 (s, 1H), 6.37 (d, 1H,
J = 15.2 Hz), 5.82 (d, 1H, J = 15.2 Hz), 4.52 (m, 2H), 3.28
(m, 1H), 2.82 (m, 1H), 2.46 (s, 3H), 2.37 (s, 3H), 2.32 (s,
3H), 2.12–2.04 (m, 3H), 1.99 (s, 6H), 1.76 (s, 3H), 1.70–
1.60 (m, 3H), 1.46–1.44 (m, 2H). 13C{1H} NMR
(100 MHz) d 181.9 (d, JRh–C = 52.5 Hz), 159.3, 155.7,
138.1, 137.1, 136.9, 136.7, 135.6, 135.1, 133.8, 129.1,
1
(400 MHz, CDCl3) d 7.79 (dd, 1H, J = 7.2 Hz, 7.2 Hz),
7.69 (d, 1H, J = 7.2 Hz), 7.17 (d, 1H, J = 7.2 Hz), 7.11
(d, 1H, J = 1.6 Hz), 7.08 (s, 1H), 6.91 (s, 2H), 6.88 (s,
1H), 6.70 (d, 1H, J = 1.6 Hz), 6.39 (d, 1H, J = 14.8 Hz),
5.92 (d, 1H, J = 14.8 Hz), 4.91–4.78 (m, 2H), 3.27 (m,
1H), 2.93 (m, 1H), 2.45 (s, 3H), 2.36 (s, 3H), 2.31 (s,
3H), 2.24–2.10 (m, 2H), 2.03–1.94 (m, 1H), 1.98 (s, 6H),
1.75 (s, 3H), 1.73–1.64 (m, 3H), 1.49–1.42 (m, 2H).
13C{1H} NMR (100 MHz) d 182.0 (d, JRh–C = 51 Hz),
159.1, 155.8, 138.0, 137.0, 136.6, 135.7, 135.1, 133.9,
129.1, 127.9, 127.7, 123.5, 122.6, 121.4, 120.9, 97.0 (d,
JRh–C = 6.9 Hz), 96.9 (d, JRh–C = 7.6 Hz), 68.8 (d, JRh–C
= 14.5 Hz), 67.5 (d, JRh–C = 14.4 Hz), 56.8, 34.1, 31.8,
29.4, 28.3, 21.4, 20.6, 20.1, 18.0. HR-FAB for [MꢂCl]+:
Calc. 606.2355 (C35H41N3103Rh), Found: 606.2357. Anal.
Calc. for C35H41N3ClRh: C, 65.47; H, 6.44; N, 6.54.
Found: C, 65.21; H, 6.69; N, 6.28%.
128.0, 127.8, 123.6, 122.9, 121.7, 120.4, 95.4 (d, JRh–C
7.6 Hz), 94.8 (d, JRh–C = 7.6 Hz), 70.2 (d, JRh–C
=
=
12.9 Hz), 69.0 (d, JRh–C = 13.7 Hz), 56.1, 33.9, 31.7, 29.6,
28.6, 21.5, 20.6, 18.4, 18.1. IR (KBr, cmꢂ1): 2038 (s), 1235
(w). Anal. Calc. for C35H41N6Rh: C, 64.81; H, 6.37; N,
12.96. Found: C, 64.66; H, 6.73; N, 12.70%.
4.2.7. (C,N-pyNꢀC)Rh(CO)2(BF4) (9)
To a solution of complex 7 (111.6 mg, 0.16 mmol) in
CH2Cl2 (30 ml) was stirring under CO (1 atm) for 3 h at
r.t. After filtrating through Celite, the solution was concen-
trated and yielded yellow solids. Recrystallization from
CH2Cl2 and hexane provided yellow solids (95.8 mg,
93%), which are suitable for single crystal X-ray diffraction
analysis. 1H NMR (400 MHz, CDCl3) d 8.28 (d, 1H,
J = 8.0 Hz), 8.11 (dd, 1H, J = 8.0 Hz, 8.0 Hz), 8.06 (d,
1H, J = 2.0 Hz), 7.41 (d, 1H, J = 8.0 Hz), 6.97 (s, 2H),
6.96 (s, 2H), 6.91 (d, 1H, J = 2.0 Hz), 6.20–5.20 (2H, br),
2.34 (s, 6H), 1.98 (s, 6H), 1.91 (s, 6H). 13C{1H} NMR
4.2.5. (C,N-pyNꢀC)Rh(COD)(BF4) (7)
A mixture of complex 6 (221.3 mg, 0.35 mmol) and silver
tetrafluoroborate (70.0 mg, 0.36 mmol) in CH2Cl2 (30 ml)
was stirred under nitrogen at the ambient temperature for
1 h. The mixture was filtrated through Celite and the filtrate
was collected and concentrated. Recrystallization from a
solution of CH2Cl2 and hexane provided the desired prod-
uct as yellow crystalline solids, which were suitable for X-
(100 MHz) d 183.2 (d, JRh–C = 70.8 Hz), 181.6 (d, JRh–C
=
54.8 Hz), 172.0 (JRh–C = 44.9 Hz), 163.3, 154.4, 141.4,
140.3, 140.2, 136.6, 135.3, 134.2, 129.2, 128.9, 128.5, 127.7,
125.7, 124.5, 123.6, 55.1, 31.0, 28.1, 21.3, 21.2, 18.0. IR
(KBr, cmꢂ1): 2933 (w), 2866 (w), 2084 (s), 2031 (s), 1620
(m), 1461 (m), 1070 (s). HR-FABMS: Calc. 554.1315
(C29H29N3O2103Rh), [M+]), 526.1366 (C28H29N3O103Rh,
1
ray single crystal diffraction analysis. (230.1 mg, 96%): H
NMR (400 MHz, CDCl3) d 8.14 (dd, 1H, J = 7.6 Hz,
1.2 Hz), 7.94–7.91(m, 2H), 7.22 (d, 1H, J = 1.6 Hz), 7.03
(s, 1H), 6.93 (s, 1H), 6.90 (s, 1H), 6.85 (s, 1H), 6.60 (d, 1H,
J = 1.6 Hz), 6.38 (d, 1H, J = 14.0 Hz), 6.17 (d, 1H,
J = 14.0 Hz), 4.68–4.64 (m, 1H), 3.81–3.79 (m, 1H), 3.63
(m, 1H), 2.66–2.60 (m, 1H), 2.48–2.40 (m, 1H), 2.35 (s,
3H), 2.33 (s, 3H), 2.31 (s, 3H), 2.06–1.93 (m, 4H), 1.89 (s,
3H), 1.86 (s, 3H), 1.64 (s, 3H), 1.64 (s, 3H), 1.43–1.39 (m,
1H), 1.23–1.14 (m, 2H). 13C{1H} NMR (100 MHz) d
174.2 (d, JRh–C = 52.5 Hz), 161.3, 154.7, 139.2, 139.0,
137.0, 136.1, 135.4, 134.8, 134.5, 128.6, 128.5, 128.1, 127.8,
127.6, 124.3, 123.3, 122.9, 98.2 (d, JRh–C = 7.6 Hz), 94.9
(d, JRh–C = 6.8 Hz), 73.5 (d, JRh–C = 13.7 Hz), 71.8 (d,
JRh–C = 12.2 Hz), 56.7, 35.4, 32.0, 29.2, 26.5, 23.4, 21.5,
21.4, 21.1, 18.6, 18.2. Anal. Calc. for C35H41N3BF4Rh: C,
60.62; H, 5.96; N, 6.06. Found: C, 60.41; H, 6.07; N, 5.95%.
[M+ꢂCO]);
Found:
554.1305
(C29H29N3O2103Rh),
526.1370 (C28H29N3O103Rh). Anal. Calc. for C29H29N3O2-
BF4Rh: C, 54.32; H, 4.56; N, 6.55. Found: C, 54.54; H,
4.85; N, 6.29%.
4.2.8. [(C-pyNꢀC)Rh(COD)(PPh3)]BF4 (10)
Complex 7 (18.5 mg, 0.027 mmol) and triphenylphos-
phine (7.0 mg, 0.027 mmol) dissolved in acetone-d6
(0.4 ml) was shaked with sonicator at room temperature
for 10 min. NMR spectrum showed the complete conver-
sion into the phosphine-substituted complex. 1H NMR
(400 MHz, CDCl3) d 7.96 (dd, 1H, J = 7.6 Hz, 7.6 Hz),
7.62–7.56 (br, 5H), 7.52–7.44 (m, 8H), 7.41 (s, 1H), 7.40
(d, 1H, J = 7.6 Hz), 7.39–7.36 (m, 3H), 7.27 (d, 1H,
J = 7.6 Hz), 7.02 (s, 1H), 7.00 (s, 1H), 6.89 (s, 2H), 6.49
(d, 1H, J = 15.6 Hz), 5.42 (m, 1H), 4.71 (d, 1H,
J = 15.6 Hz), 4.51 (m, 1H), 4.04 (m, 1H), 3.91 (m, 1H),
2.37 (s, 3H), 2.29 (s, 3H), 2.00–1.72 (m, 14H), 1.78 (s,
3H), 1.62 (s, 3H). 31P{1H} NMR (161.9 MHz) d 24.1 (d,
JRh–P = 153.5 Hz). 13C{1H} NMR (100 MHz) d 177.5
(dd, JRh–C = 50.6 Hz, JP–C = 11.8 Hz), 160.0, 155.6,
139.5, 137.7, 137.1, 136.7, 135.9, 135.4, 134.2, 131.9 (d,
4.2.6. (C-pyNꢀC)Rh(COD)(N3) (8)
Complex 6 (63.5 mg, 0.10 mmol) and sodium azide
(19.8 mg, 0.31 mmol) was dissolved in ethanol (10 ml) and
water (5 ml). The resulting solution was heat to reflux for
6 h under nitrogen. Removal of ethanol, the residue was
extracted with ethyl acetate (20 ml · 3). All organic portions
were combined and dried over MgSO4. Recrystallization
from ethyl acetate and hexane gave the desired complex in
yellow solids (50.3 mg, 79%): 1H NMR (400 MHz, CDCl3)
d 7.81 (dd, 1H, J = 7.6 Hz, 7.6 Hz), 7.58 (d, 1H, J =
JP–C = 9.9 Hz), 131.2, 129.7, 129.2, 129.1 (d, JP–C
=