A. Jakob, Y. Shen, T. Wächtler, S. E. Schulz, T. Gessner, R. Riedel, C. Fasel, H. Lang
n
126.8 (ϭCH), 127.9 (Ph), 128.9 (Ph), 129.2 (Ph), 136.4 (Ph), 141.1 (ϭCH),
Synthesis of [( Bu P)CuO CCF ] (3b)
3
2
3
31
1
1
71.8 (CO
2
3
). P{ H} NMR (CDCl ): δ Ϫ13.8.
n
Complex 3b was accessible by the reaction of [( Bu
3.01 g, 10.0 mmol) dissolved in 40 mL of diethyl ether with
CF CO K] (6) (1.52 g, 10.0 mmol) suspended in 30 mL of diethyl
3
P)CuCl] (5a)
(
[
n
Synthesis of [( Bu P) CuO CCH ] (4a)
3
2
2
3
3
2
ether at Ϫ20 °C. After 4 hours of stirring at this temperature, all
volatiles were removed in oil-pump vacuum and to the remaining
liquid 100 mL of n-pentane were added. Filtration through a pad
of Celite and evaporation of the solvent from the filtrate in oil-
pump vacuum gave a colorless liquid. Yield: 3.16 g (8.35 mmol,
nBu
3
P (2) (4.04 g, 20.0 mmol) dissolved in 40 mL of diethyl ether
CCH ] (1a) (1.23 g, 10.0 mmol) sus-
was added dropwise to [CuO
2
3
pended in 40 mL of diethyl ether at Ϫ20 °C. After 2 hours of stir-
ring, all volatiles were removed in oil-pump vacuum to leave a col-
orless liquid. Yield: 4.16 g (7.9 mmol, 79 % based on 1a). Elemental
analysis: Calcd. for C26
Found: C, 59.59; H, 10.85 %.
83 % based on 5a). Elemental analysis: Calcd. for C14
3 2
H27CuF O P
2 2
H57CuP O (527.23) C, 59.23; H, 10.90.
(378.88) C, 44.43; H, 7.20. Found: C, 44.32; H, 7.26 %.
IR (NaCl): ν [cmϪ1] 1672 (s) (CO, asym.), 1461 (vs) (CO, sym.), 1412 (m),
IR (NaCl): ν [cmϪ1] 1594 (s) (CO, asym.), 1460 (s) (CO, sym.). 1H NMR
1
1
199 (vs) (CF
3
). H NMR (CDCl
3
): δ 1.32 (m, 18 H, (CH
2
)
3
CH
3
), 0.95 (t,
14.1
(
(
(
CDCl
CH
CH
3
): δ 0.59 (t, JHH ϭ 4.3 Hz, 18 H, (CH
2
)
3
CH
). C{ H} NMR (CDCl
), 24.8 (CH CH CH CH
), 27.2 (CH CH CH CH , JPC ϭ 6.8 Hz),
): δ Ϫ25.0.
3
), 1.10 (m, 36 H,
1
3
1
J
HH
ϭ
7.4 Hz, 9 H, (CH
2
)
3
CH
), 25.0 (CH CH
, JPC ϭ 17.0 Hz), 27.4 (CH
3
).
C{ H} NMR (CDCl
3
):
δ
13
1
2
)
3
CH
3
), 1.13 (s, 3 H, CO
CH ), 24.1 (CO
CH CH CH
2
CH
3
3
): δ 13.8
(
(
CH
CH
2
CH
CH
2
CH
CH
2
CH
3
2
2
CH
2
CH
3
,
J
PC
ϭ
13.0 Hz), 25.4
, JPC ϭ 4.3 Hz),
2
CH CH
2
2
3
2
CH
3
2
2
2
3 PC
, J ϭ
2
2
2
CH
3
2
CH
2
CH
2
CH
3
1
1.1 Hz), 26.0 (CH
2
2
2
3
2
2
2
3
3
1
1
118.1 (CF
3
CO
2
, JCF ϭ 289 Hz), 161.4 (CF
): δ Ϫ18.4.
3
CO
2
, JCF ϭ 25.9 Hz). P{ H}
31
1
1
75.4 (CO
2
CH
3
). P{ H} NMR (CDCl
3
NMR (CDCl
3
n
Synthesis of [( Bu P) CuO CCF ] (4b)
3
2
2
3
n
Synthesis of [( Bu P)CuO CPh] (3c)
3
2
Complex 4b was synthesized in the same manner as 3b. In this
n
[
(
CuO
see above). In this respect, benzoic acid (1.22 g, 10.0 mmol) was
reacted with [CuCl] (0.99 g, 10.0 mmol) in presence of NEt (1.01 g,
.39 mL, 10.0 mmol). After appropriate work-up, colorless [Cu-
2
CPh] (1c) was synthesized similar to the preparation of 1a
respect, [( Bu P) CuCl] (5b) (5.03 g, 10.0 mmol) was reacted with
3
2
6 (1.52 g, 10.0 mmol). After appropriate work-up, complex 4b was
obtained as a colorless liquid. Yield: 4.88 g (8.4 mmol, 84 % based
on 5b). Elemental analysis: Calcd. for C H CuF O P (581.20)
3
1
2
6
54
3
2 2
O
2
CPh] (1c) was obtained in 1.13 g yield (61 % based on [CuCl]).
C, 53.77; H, 9.38. Found: C, 53.76; H, 9.21 %.
2
.02 g (10.0 mmol) of 2 were dissolved in 20 mL of diethyl ether
and this solution was added dropwise to the suspension of [Cu-
CPh] (1c) (1.85 g, 10.0 mmol) in 40 mL of diethyl ether at
IR (NaCl): ν [cmϪ1] 1682 (s) (CO, asym.), 1464 (vs) (CO, sym.). 1H NMR
(CDCl ): δ 1.39 [m, 36 H, (CH ) CH ], 0.82 [t, J ϭ 6.9 Hz, 18 H,
3
2 3
3
HH
CH
1
3
1
(
CH
CH
2
)
3
CH
3
]. C{ H} NMR (CDCl
3
): δ 13.9 (CH
CH ), 117.2 (CF
): δ Ϫ17.6.
2
2 2 3
CH CH ), 24.8
O
2
(
2
CH CH
2
2
CH ), 27.3 (CH CH CH
3
2
2
2
3
3
, JCF ϭ 308 Hz),
Ϫ20 °C. The reaction mixture was stirred for 2 hours at this tem-
perature. Filtration through a pad of Celite and evaporation of the
solvent from the filtrate in oil-pump vacuum gave colorless, liquid
3
1
1
1
61.5 (CO, JCF ϭ 35.0 Hz). P{ H} NMR (CDCl
3
3
c. Yield: 3.06 g (7.8 mmol, 79 % based on 2). Elemental analysis:
Calcd. for C19 32CuO P (386.98) C, 58.97; H, 8.33. Found: C,
8.76; H, 7.97 %.
n
Synthesis of [( Bu P) CuO CPh] (4c)
3
2
2
H
2
5
Complex 4c was synthesized similarly to the procedure used for the
synthesis of 3c. In this respect, 2 (4.04 g, 20.0 mmol) was reacted
with 1c (1.85 g, 10.0 mmol). After appropriate work-up, complex
4c was isolated as a colorless liquid. Yield: 4.89 g (8.3 mmol, 83 %
based on 1c). Elemental analysis: Calcd. for C31
589.30): C, 63.18; H, 10.09. Found: C, 62.78; H, 9.88 %.
IR (NaCl): ν [cmϪ1] 1705 (s) (CO, asym.), 1600 (s) (CO, sym.). 1H NMR
(
(
(
CDCl
CH
CDCl
3
): δ 0.83 (t, 9 H, JHH ϭ 7.1 Hz, (CH
CH ), 7.3 (m, 3 H, C ), 8.0 (m, 2 H, C
): 14.0 (CH CH CH CH ), 24.7 (CH CH
3.0 Hz), 25.0 (CH CH CH CH , JPC ϭ 20.2 Hz), 27.4 (CH
PC ϭ 2.8 Hz), 128.1 (Ph), 130.1 (Ph), 131.5 (Ph), 135.0 (Ph), 171.8 (CO
2 3 3
) CH ), 1.2Ϫ1.5 (m, 18 H,
1
3
1
2
)
3
3
δ
6
H
2
5
6
H
5
). C{ H} NMR
CH CH
CH
3
2
2
3
2
2
2
3 PC
, J ϭ
2 2
H59CuO P
1
2
2
2
3
2
2
CH
2
3
CH ,
(
J
2
Ph).
3
1
1
IR (NaCl): ν [cmϪ1] 1708 (s) (CO, asym.), 1654 (s) (CO, sym.). 1H NMR
P{ H} NMR (CDCl
3
): δ Ϫ14.8.
(
J
CDCl
HH ϭ 4.2 Hz, 7.9 (m, 2 H, C
δ 14.0 (CH CH CH CH
(CH CH CH CH , J ϭ 20.4 Hz), 27.3 (CH CH CH CH ), 128.0 (Ph),
3
): δ 1.1Ϫ1.4 [m, 36 H, (CH
2
)
5
3
CH
), (CH
CH
3
], 7.2 (m, 3 H, C
6
H
5
), 0.68 [t, 18 H,
]. C{ H} NMR (CDCl ):
CH , JPC ϭ 13.1 Hz), 25.0
1
3
1
6
H
2
)
3
CH
2
3
3
2
2
2
3
), 24.7 (CH
2
2
CH
3
n
Synthesis of [( Bu P)CuO CCH؍
CHPh] (3d)
3
2
2
2
2
3
PC
2
2
2
3
3
1
1
1
29.9 (Ph), 131.2 (Ph), 135.4(Ph), 171.9 (CO
2 3
). P{ H} NMR (CDCl ): δ
Cinnamic acid (1.48 g, 10 mmol) was reacted with [CuCl] (0.99 g,
0.0 mmol) in a similar manner as described above. After appropri-
ate work-up, yellow [CuO CCHϭCHPh] (1d) could be isolated in
.84 g yield (87 % based on [CuCl]). Bu
Ϫ18.5.
1
2
n
n
1
3
P (2) (2.02 g, 10.0 mmol)
Synthesis of [( Bu P) CuO CCH؍
CHPh] (4d)
3 2 2
was dissolved in 20 mL of diethyl ether and then added dropwise
to a suspension of 1d (1.84 g, 8.73 mmol) in 30 mL diethyl ether
at Ϫ20 °C. After stirring the reaction mixture for 3 hours at this
temperature, it was filtered through a pad of Celite and all volatiles
were removed in oil-pump vacuum to give a colorless liquid. Yield:
Complex 4d was accessible in an analogous way as 3d. Therefore,
n
Bu
0.0 mmol). After appropriate work-up, complex 4d could be iso-
lated as a colorless liquid. Yield: 4.67 g (7.6 mmol, 76 % based on
3
P (2) (4.04 g, 20.0 mmol) was reacted with 1d (2.11 g,
1
1d). Elemental analysis: Calcd. for C33
2 2
H61CuP O (615.34) C,
3
.39 g (8.2 mmol, 82 % based on 1a). Elemental analysis: Calcd.
for C21 34CuO P (413.02) C, 61.07; H. 8.30. Found: C, 60.78; H,
.97 %.
64.41; H. 9.99. Found: C, 63.92; H, 9.70 %.
H
2
IR (NaCl): ν [cmϪ1] 1640 (m) (CO, asym.), 1579 (s) (νCϭC), 1555 (vs) (CO,
7
1
sym.). H NMR (CDCl
3
): δ 0.89 [t, 18 H, JHH ϭ 6.8 Hz, (CH
2 3 3
) CH ], 1.5
IR (NaCl): ν [cmϪ1] 1670 (m) (νCϭC), 1639 (s) (CO, asym.), 1553 (vs) (CO,
[m, 36 H, (CH
)
3
CH
], 7.3Ϫ7.4 (m, 5 H, Ph), 6.82 (d, 1 H, CH, JHH
ϭ
2
3
1
13
1
sym.). H NMR (CDCl
3
): δ 0.84 (t, JHH ϭ 6.9 Hz, 9 H, (CH
2
)
3
CH
3
), 1.4 (m,
15.8 Hz), 7.47 (d, 1 H, CH, JHH ϭ 15.8 Hz). C{ H} NMR (CDCl
3
): δ 14.2
1
8 H, (CH
2
)
3
CH
3
), 6.45 (d, 1 H, CH, JHH ϭ 12.0 Hz), 7.2Ϫ7.4 (m, 5 H,
(CH
(CH
2
CH
CH
2
CH
CH
2
CH
3
), 25.0 (CH
, JCP ϭ 12.8 Hz), 27.4 (CH
2
CH
2
CH
2
CH
2
3
,
J
CP
ϭ
CH
12.3 Hz), 25.4
, JCP ϭ 3.5 Hz),
1
3
1
Ph), 7.50 (d, 1 H, CH, JHH ϭ 12.0 Hz). C{ H} NMR (CDCl
3
): δ 14.1
2
2
2
CH
3
CH
2
CH
2
3
(
(
CH
CH
2
CH
CH
2
CH
CH
2
CH
3
), 24.8 (CH
, JPC ϭ 15.4 Hz), 27.2 (CH
2
CH
2
CH
2
CH
2
3
,
J
PC
ϭ
CH
12.5 Hz), 25.1
126.6 (ϭCH), 127.7 (Ph), 128.5 (Ph), 128.8 (Ph), 137.2(Ph), 138.4 (ϭCH),
173.3 (CO
3
1
1
2
2
2
CH
3
CH
2
CH
2
3
, JPC ϭ 2.9 Hz),
2
). P{ H} NMR (C
6
D
6
): δ Ϫ19.4.
2232
www.zaac.wiley-vch.de
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 2226Ϫ2234
Jakob, Alexander
