Inorganic Chemistry
Article
(m, 12H). 31P{ H} NMR (121.5 MHz, C D ) δ/ppm: 15.0 (d, J
1
1
9
=
00), 264(sh) (43 800), 304 (17 000), 375 (4140). IR (Nujol): ν
̃
CN
6
6
Rh−P
−
1
−1
−1
2072 cm . Anal. Calcd for C ClH NO P Rh: C, 63.38; H, 5.72;
= 84 Hz). UV−vis (THF): λ/nm (ε/M cm ) 274 (sh) (16 900),
282 (15 500), 304 (16 200), 345 (19 500), 422 (950). IR (Nujol):
= 2220 cm . Anal. Calcd for C Cl H NP Rh: C, 51.24; H,
3.57; N: 1.27. Found: C, 51.26; H, 3.46; N, 1.25.
Complex 3c. The reaction mixture was stirred for 6 d. 87% yield; H
NMR (500 MHz, C D ) δ/ppm: 1.17 (br, m, 12H), 1.55 (br, m, 3H),
.94 (s, 18H), 6.95 (m, 12H), 8.40 (m, 12H). P{ H} NMR (121.5
MHz, C D ) δ/ppm: 15.1 (d, J
ε/M cm ) 272 (sh) (12 300), 280 (11 600), 315 (14 500), 350
16 100), 430 (904). IR (Nujol): ν
C Cl H NP Rh: C, 65.01; H, 5.87; N, 1.43. Found: C, 64.87; H,
.78; N, 1.43. Crystals suitable for single-crystal diffraction analysis
were obtained from a benzene solution of 3c layered with pentane.
Complex 3d. The reaction mixture was stirred for 13 d. 99% yield;
H NMR (500 MHz, C D ) δ/ppm: 1.21 (br, m, 6H), 1.27 (br, d,
H), 1.60 (br, m, 3H), 3.17 (s, 18H), 6.73 (m, 12H), 8.42 (m, 12H).
P{ H} NMR (121.5 MHz, C D ) δ/ppm: 13.5 (d, J
53
57
6 2
N, 1.39. Found: C, 63.12; H, 5.94; N, 1.36.
III
−1
Preparation of cis,trans-Rh Cl H(CNAd)(P(4-X-C H ) ) (2) (X
ν
̃
2
6
4 3 2
CN
47
9
39
2
=
F (2a), Cl (2b), Me (2c), OMe (2d)). Complex 1a (100 mg, 0.107
mmol) and a magnetic stirbar were added to a 20 mL scintillation vial.
The solid was dissolved in 2 mL of CH Cl to give a clear, yellow
1
2
2
6
6
31
1
solution. A solution of HCl in 1,4-dioxane (4.2 M, 0.25 mL, 10 equiv)
was added to the vial, and the mixture immediately became a clear
faintly yellow solution. The solution was then stirred at 20 °C for 1 h
before being taken to dryness in vacuo. The resultant off-white solid
was suspended in roughly 10 mL of pentane, and a few drops of a
solution of HCl in 1,4-dioxane were added to the suspension. The
mixture was stirred, and the solid became white. The contents of the
vial were allowed to settle, and the pentane was removed by pipet. The
resultant fine white solid was dried in vacuo at 20 °C to remove
1
1
= 80 Hz). UV−vis (THF): λ/nm
6
6
Rh−P
−1
−1
(
(
−1
̃
= 2214 cm . Anal. Calcd for
CN
53
3
57
2
5
1
6
6
1
residual solvent. Yield: 103 mg (99%). H NMR (500 MHz, CD Cl )
2
2
6
1
2
δ/ppm: −14.75 (dt, 1H, J
= 15.0 Hz, J
= 12.5 Hz), 1.13 (br,
31
1
1
Rh−H
P−H
= 80 Hz).
6
−1
6
Rh−P
d, 6H), 1.42 (br, m, 6H), 1.85 (br, m, 3H), 7.14 (m, 12H), 7.89 (m,
−1
UV−vis (THF): λ/nm (ε/M cm ) 275 (sh) (22 400), 284 (19
00), 327 (15 100), 359 (15 800), 431 (1090). IR (Nujol): ν
204 cm . Anal. Calcd for C Cl H NO P Rh: C, 59.20; H, 5.34; N,
1.30. Found: C, 59.15; H, 5.28; N, 1.25.
2H). 31P{ H} NMR (121.5 MHz, CD Cl ) δ/ppm: 24.3 (d, J
1
1
=
1
2
2
Rh−P
2
2
̃
=
−
1
−1
CN
9
4 Hz). UV−vis (THF): λ/nm (ε/M cm ) 262(sh) (19 400), 268
−1
53
3
57
6 2
(
(
20 000), 274(sh) (18 600), 280(sh) (15 600), 308 (14 000). IR
Nujol): ν
−1
̃
= 2124 cm . Anal. Calcd for C Cl F H NP Rh: C,
III
2
Rh−H 47 2 6 40 2
Addition of O2 to 1 To Generate trans-Rh Cl(CNAd)(η -
5
8.28; H, 4.16; N, 1.45. Found: C, 57.81; H, 4.15; N, 1.50. Crystals
O )(P(4-X-C H ) ) (4) (X = F (4a), Cl (4b), Me (4c), OMe (4d)). A
2
6 4 3 2
suitable for single-crystal diffraction analysis were obtained from a
J. Young NMR tube was charged with a yellow solution of 1a (20.0
mg, 0.0215 mmol) in 0.7 mL of THF-d at 20 °C. The tube was then
CH Cl solution of 2 in the presence of excess HCl layered with
pentane.
Complex 2b. 94% yield; H NMR (500 MHz, CD Cl ) δ/ppm:
2
2
8
flushed with O for several minutes in order to achieve 1.0 atm of O .
1
2
2
2
2
After the tube was shaken vigorously, the yellow solution rapidly
became olive-green. A P{ H} NMR spectrum obtained immediately
after the addition of O showed the quantitative generation of a single
product. Spectral data for 4a: H NMR (500 MHz, THF-d ) δ/ppm:
.40 (br, d, 6H), 1.51 (br, m, 6H), 1.89 (br, m, 3H), 7.14 (m, 12H),
.66 (m, 12H). P{ H} NMR (121.5 MHz, C D ) δ/ppm: 27.3 (d,
JRh−P = 95 Hz). UV−vis (THF): λ/nm (ε/M cm ) 269 (21 400),
275 (22 000), 290 (sh) (22 300), 304 (24 800). IR (Nujol): ν =
1
2
−
14.44 (dt, 1H, J
= 15.0 Hz, J
= 12.5 Hz), 1.09 (br, d, 6H),
31
1
Rh−H
P−H
1
.45 (br, m, 6H), 1.86 (br, m, 3H), 7.42 (m, 12H), 7.74 (m, 12H).
3
1
1
1
2
P{ H} NMR (121.5 MHz, CD Cl ) δ/ppm: 25.4 (d, J
= 94
1
2
−
2
Rh−P
1
−1
8
Hz). UV−vis (THF): λ/nm (ε/M cm ) 273(sh) (23 600), 280(sh)
1
−1
(
23 000), 314 (15 800). IR (Nujol): ν
̃
= 2102 cm . Anal. Calcd
31
1
Rh−H
7
6 6
for C Cl H NP Rh: C, 52.89; H, 3.78; N, 1.31. Found: C, 52.66; H,
3
1
−1
−1
47
8
40
2
.75; N, 1.31.
Complex 2c: 96% yield; H NMR (500 MHz, CD Cl ) δ/ppm:
1
̃
O−O
2
2
−1
1
2
892 cm .
−
14.65 (dt, 1H, J
= 15.0 Hz, J
= 12.5 Hz), 1.04 (br, d, 6H),
Rh−H
P−H
1
Complex 4b: H NMR (500 MHz, THF-d ) δ/ppm: 1.38 (br, d,
6H), 1.54 (br, m, 6H), 1.90 (br, m, 3H), 7.42 (m, 12H), 7.60 (m,
12H). P{ H} NMR (121.5 MHz, C
Hz). UV−vis (THF): λ/nm (ε/M cm ) 273 (33 200), 281 (31
00), 311 (35 900). IR (Nujol): ν
single-crystal diffraction analysis were obtained from an oxygenated
CH Cl solution of 4b layered with oxygenated pentane.
Complex 4c: H NMR (500 MHz, THF-d
H), 1.47 (br, m, 6H), 1.82 (br, m, 3H), 2.32 (s, 18H), 7.12 (m, 12H),
8
1
.38 (br, m, 6H), 1.79 (br, m, 3H), 2.36 (s, 18H), 7.20 (d, 12H), 7.67
m, 12H). 3 P{ H} NMR (121.5 MHz, CD Cl ) δ/ppm: 23.9 (d,
JRh−P = 92 Hz). UV−vis (THF): λ/nm (ε/M cm ) 270 (16 400),
1
1
(
2
2
31
1
1
1
−1
−1
6
D
6
) δ/ppm: 28.5 (d, JRh−P = 95
−1
−1
−1
2
̃
78 (15 600), 314 (14 700). IR (Nujol): νRh−H
= 2082 cm . Anal.
−1
7
̃
= 890 cm . Crystals suitable for
O−O
Calcd for C Cl H NP Rh: C, 67.38; H, 6.19; N, 1.48. Found: C,
6
53
2
58
2
7.28; H, 6.24; N, 1.46.
Complex 2d. 99% yield; H NMR (500 MHz, CD Cl ) δ/ppm:
1
2
2
2
2
1
1
2
) δ/ppm: 1.29 (br, d,
8
−
14.71 (dt, 1H, J
= 15.0 Hz, J
= 12.5 Hz), 1.11 (br, d, 6H),
Rh−H
P−H
6
1
.39 (br, m, 6H), 1.80 (br, m, 3H), 3.82 (s, 18H), 6.92 (m, 12H), 7.70
31
1
m, 12H). 3 P{ H} NMR (121.5 MHz, CD Cl ) δ/ppm: 21.9 (d,
JRh−P = 91 Hz). UV−vis (THF): λ/nm (ε/M cm ) 249 (59 700),
1
1
7.53 (m, 12H). P{ H} NMR (121.5 MHz, C D ) δ/ppm: 27.2 (d,
Rh−P = 94 Hz). UV−vis (THF): λ/nm (ε/M cm ) 273 (19 000),
81 (19 500), 293 (sh) (20 400), 313 (23 600). IR (Nujol): ν
6 6
(
2
2
1
−1
−1
1
−1
−1
J
2
̃O−O
=
2
77 (28 500), 285 (23 100), 317 (19 800). IR (Nujol): ν
̃
= 2120
Rh−H
−1
−1
886 cm .
cm . Anal. Calcd for C Cl H NO P Rh: C, 61.16; H, 5.62; N, 1.35.
Found: C, 61.09; H, 5.56; N, 1.34.
53
2
58
6
2
1
Complex 4d: H NMR (500 MHz, THF-d ) δ/ppm: 1.34 (br, d,
6H), 1.47 (br, m, 6H), 1.83 (br, m, 3H), 2.32 (s, 18H), 6.86 (m, 12H),
.57 (m, 12H). P{ H} NMR (121.5 MHz, C D ) δ/ppm: 24.1 (d,
JRh−P = 92 Hz). UV−vis (THF): λ/nm (ε/M cm ) 276 (sh) (32
00), 285 (26 700) (sh), 321 (26 300). IR (Nujol): ν
X-ray Crystallographic Details. All structures were collected on a
8
III
Preparation of trans-Rh Cl (CNAd)(P(4-X-C H ) ) (3) (X = F
3
6
4 3 2
31
1
7
(
3a), Cl (3b), Me (3c), OMe (3d)). Complex 1a (100 mg, 0.107
6
6
1
−1
−1
mmol) was added to a scintillation vial along with a magnetic stirbar.
The solid was dissolved in 2 mL of CH Cl to give a clear yellow
−1
6
̃
= 888 cm .
O−O
2
2
solution. A solution of PhICl (29.4 mg, 0.107 mmol, 1.00 equiv) was
2
added to the vial to give a yellow-orange solution. The contents of the
vial were stirred at 20 °C for 30 min before being taken to dryness in
vacuo. The resultant yellow-orange solid was washed with 3 × 10 mL
portions of pentane and then pumped in vacuo at 20 °C overnight to
Bruker three-circle platform goniometer equipped with an Apex II
CCD and an Oxford cryostream cooling device at 100 K. Radiation
was generated from a graphite fine focus sealed tube Mo Kα (0.71073
Å) source. Crystals were mounted on a cryoloop using Paratone N oil.
Data were integrated using SAINT and scaled with a multiscan
absorption correction using SADABS. The structures were solved by
direct methods or Patterson methods using SHELXS-97 and refined
1
give a fine yellow-orange solid. Yield: 105 mg (97%). H NMR (500
MHz, C D ) δ/ppm: 1.12 (br, d, 6H), 1.16 (br, m, 6H), 1.55 (br, m,
6
6
3
1
1
3
H), 6.73 (m, 12H), 8.13 (m, 12H). P{ H} NMR (121.5 MHz,
1
2
C D ) δ/ppm: 15.2 (d, J = 83 Hz). UV−vis (THF): λ/nm (ε/
against F on all data by full matrix least-squares with SHELXL-97. All
6
6
Rh−P
−
1
−1
M
4
cm ) 268 (14 300), 276 (14 200), 298 (14 200), 342 (14 000),
non-hydrogen atoms were refined anisotropically. Hydrogen atoms
bound to carbon were placed at idealized positions and refined using a
riding model. For hydride complex 2, the rhodium-bound hydrogen
atom was tentatively located in the difference map and refined
isotropically. For 2a, the adamantyl group was modeled as a two-part
positional disorder, and rigid bond restraints were used on all
−
1
19 (960). IR (Nujol): ν
̃
= 2223 cm . Anal. Calcd for
CN
C Cl F H NP Rh: C, 56.28; H, 3.92; N, 1.40. Found: C, 55.97; H,
4
7
3
6
39
2
3
.95; N, 1.40.
Complex 3b. 98% yield; H NMR (500 MHz, C D ) δ/ppm: 1.09
1
6
6
(
br, d, 6H), 1.23 (br, m, 6H), 1.62 (br, m, 3H), 7.03 (m, 12H), 8.04
C
Inorg. Chem. XXXX, XXX, XXX−XXX