ˇ
M. Lama cˇ , I. Císa rˇ ová, P. St eˇ pni cˇ ka
FULL PAPER
Preparation of Dichlorido{(R,R
yl]ferrocenecarboxylic acid}(η -pentamethylcyclopentadienido)rhodi-
um(III) (9): A solution of acid 1 (90 mg, 0.20 mmol) in chloroform
p
)-2-[1-(diphenylphosphanyl-κP)eth-
one (3 mL) was added to a solution of [Rh(acac)(CO)(PCy )]
3
5
(51 mg, 0.10 mmol) in butan-2-one (5 mL) and the mixture was
heated at reflux for 5 min. The reaction solution was cooled to
room temperature and volatiles were removed under vacuum to
5
(
(
5 mL) was added to a solution of [{(µ-Cl)RhCl(η -C
62 mg, 0.10 mmol) in the same solvent (5 mL) and the resulting
5
Me
5
)}
2
]
1
afford 11 as a yellow solid in quantitative yield (85 mg). H NMR
clear mixture was stirred at room temperature overnight. The solu-
tion was filtered through a PTFE syringe filter (0.45 µm pore size)
and the solvents were evaporated to dryness under vacuum to give
(CDCl
H, C
3
): δ = 1.12–2.24 (m, 34 H, PCy
3
and CHCH
), 4.16 (s, 5 H,
), 4.72 (m, 1 H,
) ppm; the CHCH signal is ob-
C{ H} NMR (CDCl ): δ = 13.91 (dd,
), 26.57 (s, PCy γ-CH ), 27.56
3
), 3.31 (m, 1
5
H
3
), 3.96 (apparent t, J ≈ 2.5 Hz, 1 H, C H
5 3
3
2
C
C
5
H
H
5
), 4.20 (dq, JH,H ≈ JP,H ≈ 7 Hz, 1 H, CHCH
), 7.31–7.69 (m, 10 H, PPh
3
the product as a red glassy solid in practically quantitative yield
5
3
2
3
1
13
1
(
1
3
150 mg) according to NMR spectroscopy. H NMR (CDCl
3
): δ =
scured by those of PCy
3
.
3
3
3
2
3
.18 (br. s, 15 H, C
H, CHCH ), 4.08 (br. s, 1 H, C
), 4.58 (m, 1 H, C
H,H ≈ JP,H ≈ 7.5 Hz, 1 H, CHCH ), 7.28–8.12 (m, 10 H, PPh
): δ = 8.43 (C Me ), 20.30 (br. s, ≈ 1 Hz, C
), 37.28 (br. s, CHCH ), 67.81 (C C-COOH), 69.40 = 9 Hz, C
CH), 69.60 (C CH), 71.06 (C ), 74.81 (C CH), 127.43, 128.75 (2ϫd, JP,C = 9 Hz, PPh
4.19 (br. s, C C-CH), 98.77 (dd, JRh,C = 7, JP, C = 2 Hz, = 38, JRh,C = JP,C ≈ 3 Hz, PPh
Me ), 127.00, 127.81 (2ϫd, JP,C = 10 Hz, PPh
30.71 (2ϫs, PPh CH
), 134.22, 136.84 (2ϫd, 2JP,C = 9 Hz, PPh
CH ), 176.96 (br. s, COOH) ppm; (PPh ipso) signals not observed.
5
Me
5
), 1.89 (br. dd, JH,H = 7.5, JP,H = 18.6 Hz,
J
P,C = 2, JRh,C = 6 Hz, CHCH
3
3
2
), 4.24 (dd, JP,C = 2, 3JRh,C = 10 Hz, PCy
2
α-CH
J
), 29.12 (dd, JP,C = 14,
P,C = 37 Hz, PCy β-CH ),
CH), 66.01 (C CH), 66.72 (d, JP,C
), 71.71 (C
1
3
5
H
3
), 4.13 (s, 5 H, C
5
H
5
3
2
2
3
(
apparent t, J ≈ 2.7 Hz, 1 H, C
5
H
3
5
H
3
), 4.86 (dq,
JRh,C = 3 Hz, CHCH
3
), 30.18 (d,
3
2
3
2
1
J
3
2
)
33.36 (d, JP,C = 19 Hz, PCy
CH), 70.44 (C
C-COO), 85.90 (d,
3
5 3
H
H
5 3
ppm. 13C{ H} NMR (CDCl
CHCH
(
9
C
1
1
H
H
5
CH), 84.27 (d, JP,C
P, C = 2 Hz, C C-CH),
CH ), 128.92 (ddd, JP,C
ipso), 129.45, 130.75 (2ϫd, JP,C
), 131.53 (d, JP,C = 10 Hz, PPh CH ), 132.67
P,C = 12 Hz,
3
3
5
5
5
3
5
2
3
3
5
H
3
5
H
3
J
5 3
H
3
1
C
5
H
3
5
H
3
5
H
5
5
H
3
2
m
1
2
2
3
4
5
H
3
2
C
3
2
5
5
2
CH
m
), 130.43,
= 2 Hz, PPh
2
CH
p
2
o
1
2
2
p
2
(dd,
PPh
J
P,C = 32, J = 2 Hz, PPh Cipso), 135.76 (d, J
2
1
2
o
1
2
C
2
CH
o
), 175.14 (COO), 190.20 (dt, JRh,C = 73, JP,C = 16 Hz,
3
1
1
31
1
1
P{ H} NMR (CDCl
3
): δ = 34.3 (br. d, JRh,P = 140 Hz) ppm. IR
CϵO) ppm. P{ H} NMR (CDCl
3
): δ = 40.9 (dd, JRh,P = 125,
), 46.5 (dd, JRh,P = 127, JP,P = 319 Hz, PCy
2
1
2
(Nujol): ν˜ = 1664 (composite s), 1299 (m), 1216 (m), 1157 (m),
JP,P = 319 Hz, PPh
2
3
)
1
4
095 (m), 1021 (w), 1000 (w), 823 (w), 747 (s), 699 (m), 610 (w),
ppm. IR (Nujol): ν˜ = 1959 (vs), 1612 (s), 1321 (s), 1244 (w), 1174
–1
35
56 103
91 (m) cm . HR MS (ESI–): calcd. for C35
H37 Cl
2
Fe RhO
2
P
(w), 1101 (w), 997 (w), 815 (w), 785 (w), 745 (m), 721 (m), 708 (m),
+
–
–1
+
[M – H ] 749.0313; found 749.0402; the observed isotopic distri-
694 (w), 593 (w), 532 (m) cm . MS (FAB+): m/z = 853 [M + H] ,
+
56 103
bution matched the calculated one.
824 [M – CO] . HR MS calcd. for C44
H] 853.2109; found 853.2079.
H
56 Fe RhO
3
P
2
[M +
+
Preparation of Chlorido{(R,R
ferrocenecarboxylato-κ O,P}(η -pentamethylcyclopentadienido)rho-
p
5
)-2-[1-(diphenylphosphanyl)ethyl]-
2
3
(η -Allyl)palladium Complexes with 6. An in situ NMR Study:
dium(III) (10): Chloroform solutions (5 mL each) of 1 (90 mg,
Amide 6 (11 mg, 0.02 mmol) was added to a solution of [{Pd(µ-
5
3
0
.20 mmol) and [{(µ-Cl)RhCl(η -C
5
Me
5
)}
2
] (62 mg, 0.10 mmol) Cl)(η -C
3
H
5
)}
2
] (3.7 mg, 0.01 mmol) in CDCl
3
(1 mL). The mixture
were mixed and the mixture was stirred at room temperature for was stirred in the dark for 1 h, then filtered through a PTFE sy-
2
h. Neutral chromatography grade alumina (ca. 2 g) was added to
ringe filter (0.45 µm) and the filtrate used directly for NMR mea-
the solution and stirring was continued overnight. The alumina was
then filtered off and washed thoroughly with chloroform. The li-
quid phase was concentrated under vacuum to give the product as
a red glassy solid. Yield: 134 mg (94%). According to the NMR
spectra, the product was an approximately 9:1 mixture of diastereo-
isomers. Note: An identical product mixture was formed when the
solution containing in situ generated 9 was filtered through a short
silica gel column. IR (Nujol): ν˜ = 1581 (s), 1307 (s), 1234 (w), 1171
surements. The sample used for IR measurements was obtained by
concentrating the reaction mixture under vacuum. H NMR
1
3
3
(CDCl
CHCH
4.16 (s, 5 H, C
3
, 50 °C): δ = 1.83 (dd, JP,H = 18.0, JH,H = 7.2 Hz, 3 H,
2
H,H = 14.8, 3JH,H = 4.9 Hz, 1 H, CH
), 4.31 (m, 1 H, C ), 4.46
(dd, JH,H = 14.8, JH,H = 6.6 Hz, 1 H, CH Ph), 5.01 (dq, JH,H
), 5.47 (br. t, JH,H ≈ 6 Hz, 1 H, NH),
and CH Ph) ppm; the remaining three
signals of the allyl moiety and one C resonance are observed
as broad bands between δ = 2.1 and 3.1 ppm and at δ ≈ 4.93 and
3
), 4.00 (dd,
J
2
Ph),
5
H
5
), 4.21 (m, 1 H, C
5
H
3
5 3
H
2
3
3
2
≈
2
3
JP,H ≈ 7 Hz, 1 H, CHCH
3
7.06–7.94 (m, 15 H, PPh
2
2
(
w), 1095 (m), 1044 (vw), 1025 (w), 999 (w), 816 (m), 746 (vs), 699
5 3
H
–1
(s), 662 (w), 526 (s), 496 (m), 460 (m) cm . HR MS (ESI+): calcd.
35
56 103
+
31
1
for C35
H
38 Cl Fe RhO
2
P [M + H] 715.0702; found 715.0713.
): δ = 1.46 (d, 2JRh,H = 3.3 Hz, 15 (Nujol): ν˜ = 3314 (m br.), 1639 (s), 1522 (s), 1302 (m), 1266 (m),
), 1.52 (dd, JH,H = 7.3, 3JP,H = 13.9 Hz, 3 H, CHCH
), 1234 (m), 1104 (m), 1099 (m), 1003 (m), 821 (m), 746 (m), 697 (vs),
.22 (m, 1 H, C ), 3.72 (apparent t, J ≈ 2.6 Hz, 1 H, C ), 4.07
s, 5 H, C ), 4.67 (dq, P,H ≈ 7.5 Hz, 1 H, CHCH ),
.76 (m, 1 H, C ), 7.16–7.98 (m, 10 H, PPh
NMR (CDCl ): δ = 9.02 (d, JRh,C ≈ 1 Hz, C
3
5.40 ppm. P{ H} NMR (CDCl , 50 °C): δ = 35.3 (s) ppm. IR
1
Major isomer: H NMR (CDCl
3
3
H, C
3
(
4
5
Me
5
3
–
1
5
H
3
5
H
3
609 (m), 514 (m), 482 (s), 460 (m) cm . MS (ESI+): m/z = 678
3
2
+
5
H
5
J
H,H
≈
J
3
[M – Cl] ; the isotopic envelope agrees with the calculated one.
1
3
1
5
H
3
2
) ppm. C{ H}
), 14.16 (d, 2JP,C
), 33.90 (d, JP,C = 18 Hz, CHCH ), 67.89 (d, J ≈
, CH), 68.18 (C CH), 70.17 (C
P,C = 2.5 Hz, C C-COO), 88.18 (d,
p
Preparation of (SP-4-2)-{(R,R )-N-Benzyl-2-[1-(diphenylphos-
2
3
5
Me
5
2
phanyl)ethyl]ferrocenecarboxamido-κ O,P}chloro(methyl)palla-
dium(II) (13): A solution of amide 6 (64 mg, 0.12 mmol) in dichlo-
romethane (5 mL) was added to a solution of [PdCl(Me)(cod)]
1
=
1
7 Hz, CHCH
Hz, C
3
3
5
H
3
5
H
3
5
H
5
), 72.09 (C
5
H
=
3
3
2
CH), 77.61 (d,
5
1
J
5
H
3
J
P,C
(
33 mg, 0.12 mmol) in the same solvent (5 mL) and the mixture
1
2
Hz, C
5
H
3
1
C-CH), 98.25 (dd, JRh,C = 7, JP,C = 3 Hz, C
25.20 (d, JP,C = 41 Hz, PPh
5
3
Me
5
),
was stirred in the dark for 20 h. The reaction solution was then
filtered through a PTFE syringe filter (0.45 µm). The product crys-
tallised upon diffusion of diethyl ether to afford 12 as an orange
crystalline solid, which was filtered off and dried in vacuo. Yield:
2
C
ipso), 127.14, 127.48 (2ϫd, JP,C
=
4
1
0 Hz, PPh
2
CH
m
), 130.22 (d, JP,C = 2 Hz, PPh
ipso), 131.04 (d, 4
P,C = 2 Hz, PPh
CH ), 180.14 (COO) ppm.
): δ = 52.0 (d, JRh,P = 148 Hz) ppm. Minor
): δ = 49.8 (d, 1JRh,P = 146 Hz) ppm.
2
CH
p
), 130.84 (d,
1
J
P,C = 38 Hz, PPh
33.93, 135.30 (2ϫd, JP,C = 9 Hz, PPh
P{ H} NMR (CDCl
2
C
J
2
CH ),
p
2
1
2
o
1
3
6
0 mg (70%). H NMR (CDCl
3
3
): δ = 0.60 (d, JP,H = 2.8 Hz, 3 H,
3
1
1
1
3
3
PdCH
3
), 1.41 (dd, JP,H = 11.5, JH,H = 7.2 Hz, 3 H, CHCH
3
), 3.43
isomer: 31P{ H} NMR (CDCl
1
3
(
m, 1 H, C
5
H
3
), 4.04 (s, 5 H, C
5 5 5 3
H ), 4.05 (m, 1 H, C H ), 4.16 (dq,
3
2
2
3
Preparation of (SP-4-2)-Carbonyl{(R,R
yl)ethyl]ferrocenecarboxylato-κ O,P}(tricyclohexylphosphane)rho-
dium(I) (11): A solution of acid 1 (45 mg, 0.10 mmol) in butan-2-
p
)-2-[1-(diphenylphosphan-
JH,H ≈ JP,H ≈ 7.5 Hz, 1 H, CHCH
3
), 4.68 (dd, JH,H = 14.4, JH,H
2
2
= 5.1 Hz, 1 H, CH
14.4, JH,H = 6.5 Hz, 1 H, CH
2
5 3 H,H
Ph), 4.99 (m, 1 H, C H ), 5.14 (dd, J =
3
3
2
Ph), 7.15 (br. t, JH,H ≈ 6 Hz, 1 H,
2284
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 2274–2287
Lamac, Martin
