Fluorous Dialkoxy-Diamino Zirconium Complexes
FULL PAPER
1
1
H NMR (500 MHz, [D
.18 (m, 8H; m-H, a and b), 6.92 (t, J=7.3 Hz, 1H; p-H, a or b), 6.88 (t,
8
]toluene, 298 K): d=7.32 (m, 8H; o-H, a and b),
3
(brs, 6H; NCH ); H resonances due to ZrCHHPh overlap those of
3
19
1
7
Ph
ꢀ79.5 (brm, 12F; CF
20.4 Hz, 4F; p-F B(C
); H NMR (400 MHz, [D
1H; p-H(ZrBn)), 7.80 (m, 2H; m-H
ZrCH Ph), 3.06 (d, J=9.4 Hz, 1H; ZrCH
2.36 ppm (s, 3H; NCH ); resonances due to CH
range of 3.01–2.59 ppm and those of NCH (CF
3.34 ppm, but are too broad to be attributed, resonances arising from o-
3
CCH
2
Ph; F{ H} NMR (376 MHz, [D
), ꢀ134.2 (m, 8F; o-F B
), ꢀ168.6 ppm (t,
5
]chlorobenzene, 290 K): d=
3
2
ꢀ
3
J=7.3 Hz, 1H; p-H, a or b), 2.97 (d, J=15.0 Hz, 2H; NCHHC
A
H
R
U
G
3
)
2
,
3
A
H
R
U
G
6
F
5
)
4
), ꢀ164.6 (q, JF,F
=
2
2
ꢀ
3
a), 2.91 (d, J=15.6 Hz, 2H; NCHHC
2
2
reomer and protons of the NCH
or b), 2.49–2.47 (d, J=10.3 Hz, 2H; ZrCHHPh, a or b), 2.49–2.47 (d,
A
H
R
U
G
3
)
2
A
T
U
G
6
F
5
)
4
2
ꢀ
1
H; NCHHC
A
C
H
T
R
E
U
N
G
(CF
3
)
2
A
H
R
U
G
6
F
5
)
4
5
]chlorobenzene, 220 K): d=8.00 (m,
2
A
H
R
U
G
ACHTREUNG
2
2
3
group, J=10.3 Hz, 2H; ZrCHHPh, a
2
2
3
2
3
2
2
overlaps the signal from the benzylic protons of the other diastereomer,
2
C
A
H
R
U
G
3 2
)
2
J=9.8 Hz, 2H; ZrCHHPh, a or b), 2.49–2.47 (m, overlaps the signals
2
13
1
from the benzylic protons, 2H; NCHCHN, a), 2.33 (d, J=15.6 Hz, 2H;
H
A
H
R
U
G
3
CCH
2
Ph; C{ H} NMR (100 MHz,
(ZrBn)), 139.7 (o-C(ZrBn)),
C-F =291 Hz, 2C;
Ph), 62.7 (2C;
), 55.6 (1C;
6 5
, o-C F ,
NCHHC
NCHCHN, b), 1.81 (s, 6H; NCH
H; Cy, a), 1.16 (brm, 4H; Cy, b), 1.05 (brm, 2H; Cy, a), 0.48 (brm, 4H;
A
C
H
T
R
E
U
N
G
(CF
3
)
2
, a or b), 2.16 (m, overlaps the signals from toluene, 2H;
5
A
H
R
U
G
ACHTREUNG
1
3
, b), 1.64 (s, 6H; NCH , a), 1.24 (brm,
3
A
H
R
N
A
T
E
N
J
1
2
3
J
3
2
1
13
Cy, A), 0.32 ppm (brm, 4H; Cy, b); { H} C NMR (125 MHz,
]toluene, 298 K): d=145.9 (Cipso, a or b), 144.9 (Cipso, a or b), 128.8 (o-
C, m-C, a or b), 128.4 (o-C, m-C, a or b), 128.2 (o-C, m-C, a or b), 127.9
o-C, m-C, a or b), 125.5 (CF , signals from a overlap signals from b),
22.8 (p-C, a or b), 122.1 (p-C, a or b), 85.0 (C(CF , a), 84.9 (C(CF
b), 72.5 (CH Ph, a or b), 69.8 (CH Ph, a or b), 66.1 (NCHCHN, Cy, b),
2.9 (NCHCHN, Cy, a), 57.5 (NCH (CF , a), 54.7 (NCH (CF , b),
4.2 (NCH , b), 38.1 (NCH , A), 24.2 (Cy, a), 23.3 (Cy, b), 23.1 (Cy, a),
2.7 ppm (Cy, b); F NMR (188 MHz, [D
NCH
NCH
2
3
C
A
H
E
N
(CF
3
)
2
2
2
2
2
[
D
8
3
A
T
U
G
3
)
2
1
1
m-C
[D
6
F
5
,
6
F
5
B
ꢀ
19
1
(
1
3
5
A
H
R
U
G
6
F
5
)
4
); F{ H} NMR
), ꢀ79.6 (m,
A
H
R
U
G
3
)
2
A
T
E
N
3
)
2
,
5
]chlorobenzene, 220 K): d=ꢀ79.2 (m, 3F; CF
3
2
2
3
), ꢀ80.1 (m, 3F; CF
3
), ꢀ81.1 (3F; CF
3
), ꢀ134.4 (m, 8F; o-F B-
ꢀ
ꢀ
6
4
2
C
A
H
R
U
G
3
)
2
2
C
A
H
E
N
3
)
2
A
H
E
N
6
F
F
5
)
)
4
), ꢀ163.8 (m, 4F; p-F B
A
H
R
U
(C
6
F
5
)
4
), ꢀ167.9 ppm (m, 8F; m-F B-
4ꢀ
3
2
[24]
1
3
3
A
H
R
U
6
5
); resonances for Ph
CCH
Ph:
H NMR: d=7.40 (m, 12H; o-
1
9
3
2
8
]toluene, 298 K): d=ꢀ74.3 (q,
H and m-H
A
H
R
U
G
3
3
A
H
R
U
G
3
)), 7.18 (t, J=8.0 Hz, 1H; p-
4
4
3
J
J
F,F =10.3 Hz, 6F; a or b), ꢀ76.7 (q, JF,F =10.3 Hz, 6F; a or b), ꢀ77.1 (q,
H(Bn)), 7.10 (t, J=8.0 Hz, 2H; m-H(Bn)), 6.72 (d, J=8.0 Hz, 2H; o-
4
4
13
1
F,F =10.3 Hz, 6F; a or b), ꢀ78.0 ppm (q, JF,F =10.3 Hz, 6F; a or b); ele-
H(Bn)), 3.96 ppm (s, 2H; CH
(CPh )), 141.2 (ipso-(Bn)), 135.1 (o-C(Bn)), 132.1 (o-C
(CPh )), 128.5 (m-C(Bn)), 127.0 (p-C(Bn and CPh
(CPh CH Ph), 45.6 ppm (CPh CH Ph).
2
(Bn)); C{ H} NMR: d=146.6 (ipso-C-
(CPh )), 129.2 (m-
)), 58.0
mental analysis calcd (%) for C30
found: C 45.98, H 4.12, N 3.54.
H
34
F
12
N
2
O
2
Zr: C 46.56, H 4.43, N 3.62;
A
H
R
U
G
3
A
H
R
U
G
3
C
A
H
R
U
G
3
3
Cy
[
0
Ti
A
C
H
T
R
E
U
N
G
(OiPr)
2
A
C
H
T
R
E
U
N
G
(ON NO)] (4):
A
solution of diamino-diol
2
(0.100 g,
3
2
3
2
2
.199 mmol) in toluene (2 mL), cooled to ꢀ308C, was added dropwise
Reaction of [Zr
ionic complex [Zr
Teflon-valved NMR tube was charged with complex
41.68 mmol) and (THF)·B(C (0.025 g, 42.80 mmol),
[D ]dichloromethane (ca. 0.5 mL) was vacuum-transferred into the mix-
A
H
R
U
G
2
Ph)
2
A
T
E
G
A
T
E
N
6
F
5
)
3
—generation of
(C (6):
(0.030 g,
and
2
over 5 min under vigorous stirring to a solution of [Ti(OiPr) ] (0.056 g,
0
slowly warmed to room temperature over 12 h under magnetic stirring.
Volatiles were removed under vacuum and the solid residue was washed
with pentane and dried in vacuo to give 4 as a white solid (0.121 g, 92%).
Elemental analysis calcd (%) for C22
found: C 40.11, H 5.05. At 298 K, two sets of signals were observed in
the H, { H} C, and F NMR spectra, consistent with the existence of
two isomers of 4 (a and b) formed in a ratio 1:6. H NMR (500 MHz,
A
H
R
U
G
4
A
H
R
N
2
Ph)
(ON NO)
2
B
A
H
R
U
G
6
F
5
)
H
3
]
A
.199 mmol) in toluene (2 mL) cooled to ꢀ308C. The clear mixture was
A
H
R
U
G
2
ture at ꢀ508C. The tube was sealed and kept at ꢀ408C for 1 h. The
H
34
F
12
N
2
O
4
Ti: C 39.65, H 5.14;
NMR data indicated quantitative and clean conversion of H to ionic spe-
1
cies 6. H NMR (500 MHz, [D
J=7.2 Hz, 2H; m-H, cation), 7.36 (t, J=7.2 Hz, 1H; p-H, cation), 7.23
(m, 2H; o-H, cation), 6.91 (t, J=7.3 Hz, 2H; m-H, borate), 6.83 (t, J=
7.3 Hz, 1H; p-H, borate), 6.72 (d, J=7.3 Hz, 2H; o-H, borate), 3.75 (d,
2
]dichloromethane, 243 K): d=7.55 (brt,
1
1
13
19
2
2
1
2
2
2
2
[
(
D
sept,
8
]toluene, 298 K): d=4.94 (sept, JH,H =6.2 Hz, 2H; CH OiPr, b), 4.91
2
2
J
H,H =6.2 Hz, 2H; CH OiPr, a), 3.07 (d,
J
H,H =16.0 Hz, 2H;
(CF , b), 2.98 (d,
, b), 2.80 (m, 2H; (Me)NCHCHN(Me),
overlaps the signal from THF, 1H; NCH
CH , THF), 3.59 (d, overlaps the signal from THF, 1H; NCH
3.58 (brm, 2H; a-CH
15.8 Hz, 1H; NCH
3.20 (m, overlaps the resonances from the ZrCH
NCH CH N), 3.13–3.10 (m, 1H; ZrCH Ph), 3.00 (m, overlaps the signals
from NCH CH N and NCH , 1H; ZrCH Ph), 3.98 (m, overlaps the reso-
nances from NCH , 2H; NCH CH N), 2.95 (s, 3H; NCH ), 2.78 (brs,
2H; BCH Ph), 2.51 (s, 3H; NCH ), 1.83 (brm, 2H; b-CH , THF),
1.63 ppm (brm, 2H; b-CH THF); C{ H} HMBC/HMQC NMR
(125 MHz, [D ]dichloromethane, 233 K): d=148.4 (Cipso, Ph, borate),
131.1 (Ph, cation), 129.4 (Ph, cation), 128.6 (Ph, borate), 126.9 (Ph,
borate), 124.8 (CF ), 124.7 (CF ), 123.8 (CF ), 122.5 (Ph, borate), 121.2
(CF ), 85.0 (C(CF ), 84.8 (C(CF , 80.3 (ZrCH Ph), 77.1 (a-CH
THF), 64.5 (NCH (CF ), 62.7 (NCH (CF ), 62.4 (NCH CH N),
57.6 (NCH CH N), 53.4 (NCH ), 46.9 (NCH ), 26.0 ppm (b-CH , THF);
the quaternary ipso-C and another signal from the benzyl group of the
2
C
A
H
R
U
G
3 2
(CF ) ), 3.72 (brm, 2H; a-
2
NCH
2
C
A
C
H
T
R
E
U
N
G
(CF
H,H =14.8 Hz, 2H; NCH
b), 2.67 (m, 2H; (Me)NCHCHN(Me), a), 2.60 (d,
NCH (CF , a), 2.50 (s, 6H; NCH , a), 2.23 (s, 6H; NCH
brm, CH
3
)
2
, a), 3.04 (d, JH,H =14.8 Hz, 2H; NCH
2
C
A
H
R
U
3
)
2
2
2
C
A
C
H
T
R
E
U
N
G
(CF
3
2
)
2
),
2
J
2
C
A
T
E
N
(CF
3
)
2
2
, THF), 3.56 (d, overlaps the signal from THF, J=
2
2
J
H,H =16.0 Hz, 2H;
, b), 1.45
OiPr, a), 1.37
2
C
A
H
R
U
G
3
)
2
), 3.43 (d, J=15.8 Hz, 1H; NCH
2
C
A
C
H
T
R
E
U
N
G
3 2
(CF ) ),
2
C
A
C
H
T
R
E
U
N
G
3
)
2
3
3
2
group, 2H;
2
(
(
2
Cy, a and b), 1.38 (d,
J
H,H =6.3 Hz, 6H; CH
3
2
2
2
2
2
d,
J
H,H =5.6 Hz, 6H; CH
OiPr, b), 1.31 (d,
J
H,H =6.3 Hz, 6H; CH
3
2
2
3
2
2
OiPr, a), 1.26 (d,
J
H,H =5.6 Hz, 6H; CH
3
OiPr, b), 0.65 ppm (brm, CH
2
3
2
2
3
1
13
Cy, a and b); { H} C NMR (125 MHz, [D
8
]toluene, 298 K): d=125.2 (q,
(CF , a and b), 79.5 (CH OiPr,
a), 79.2 (CH OiPr, b), 65.3 (NCHCHN Cy, a), 60.4 (NCHCHN Cy, b),
2
3
2
1
13
1
J
C,F =299 Hz, CF
3
, a and b), 85.5 (br, C
A
H
R
U
G
3
)
2
2
,
2
5
(
2
8.1 (NCH
2
C
A
C
H
T
R
E
U
N
G
(CF
3
)
2
, b), 54.0 (NCH
2
C
A
H
R
U
G
3
)
2
, a), 45.7 (NCH , a), 39.3
OiPr, a), 24.4 (CH OiPr, b),
1
3
NCH , b), 25.0 (CH
3
3
3
3
3
3
3
1
9
3.6 (CH
2
Cy, a), 22.5 (CH
2
Cy, b), 22.3 ppm (CH
2
Cy, a). F{ H} NMR
3
A
H
R
U
G
3
)
2
A
H
R
U
G
3
)
2
2
2
,
4
(
188 MHz, [D
8
]toluene, 298 K): d=ꢀ72.7 (q, JF,F =12.1 Hz, 6F; b), ꢀ74.4
q, JF,F =11.9 Hz, 6F; a), ꢀ75.0 (q, JF,F =12.1 Hz, 6F; b), ꢀ76.6 ppm (q,
F,F =11.9 Hz, 6F; a).
(CH Ph)
ation of ionic complex of [Zr
valved NMR tube was charged with [Zr
8.9 mmol) and [Ph C][B(C
]chlorobenzene (ca. 0.5 mL) was vacuum transferred into this mixture
2
C
A
H
R
U
G
3
)
2
2
C
A
H
E
N
3
)
2
2
2
4
4
(
2
2
3
3
2
4
J
1
9
2
6 5
cation as well as C F carbon signals were not observed; F NMR
Reaction of [Zr
A
C
H
T
R
E
U
N
G
2
2
A
H
R
U
G
3
C][B
(C
A
T
E
N
6
F
5
)
4
]—Gener-
4
2
(282 MHz, [D ]dichloromethane, 243 K): d=ꢀ77.3 (q, J =9.7 Hz, 6F),
(CH
A
H
R
U
G
6
F
5
)
4
2
F,F
4
3
2
ꢀ77.8 (brq, 3F), ꢀ79.1 (q,
J
F,F
=9.7 Hz, 3F), ꢀ131.5 (d, JF,F =20.8 Hz,
3
3
3
F), ꢀ164.3 (t,
J
F,F =20.8 Hz, 6F), ꢀ167.3 ppm (t,
JF,F =20.8 Hz, 6F);
1
[
3
A
H
R
U
G
6 5 4
F ) ]
1
1
B NMR (128 MHz, [D
2
]dichloromethane, 243 K): d=ꢀ13.2 ppm (brs,
D
5
ꢀ
[
PhCH
2
B
A
H
R
N
(C
6
F
5
)
3
] ).
at ꢀ508C. The tube was sealed and kept at ꢀ408C. A yellow solution
1
Cy
formed within 5 min. Its H NMR spectrum was recorded at 220 K and
Reaction of [Zr
ionic complex “[Zr
Teflon-valved NMR tube was charged with complex
25.85 mmol) and (THF)·B(C (0.016 g,
[D ]dichloromethane (ca. 0.5 mL) was vacuum-transferred into the mix-
A
H
R
U
G
2
Ph)
2
A
H
R
N
(ON NO)] (3) with B
A
H
R
U
G
6 5 3
F ) —generation of
Cy
indicated quantitative conversion of H to give mainly (>90%) 5. Com-
pound 5 is not soluble in hydrocarbons (toluene, pentane, hexanes).
NMR (500 MHz, [D
2
A
H
R
U
G
2
Ph)
A
H
R
U
G
A
H
R
U
G
A
H
R
U
G
2
B
A
H
R
U
(C
6
F
5
)
3
]” (7): A
1
H
3
(0.020 g,
2
5
]chlorobenzene, 290 K): d=3.39 (d, J=14.4 Hz,
A
H
R
U
G
6
F
5
)
3
27.39 mmol),
and
2
2
H; NCH
2
C
A
C
H
T
R
E
U
N
G
(CF
3
)
2
), 3.34 (d, J=9.3 Hz, 1H; ZrCH
2
Ph), 3.31 (d, J=
), 3.07 (d, J=9.3 Hz, 1H; ZrCH Ph), 2.91 (d,
CH ), 2.56 ppm
2
2
1
1
4.4 Hz, 2H; NCH
2
C
A
C
H
T
R
E
U
N
G
(CF
3
)
2
2
ture at ꢀ508C. The tube was sealed and kept at ꢀ408C for 1 h. H and
2
2
19
J=11.4 Hz, 2H; CH
2
CH
2
), 2.71 (d, J=11.4 Hz, 2H; CH
2
2
F NMR spectroscopy indicated quantitative conversion of 3 to a mix-
Chem. Eur. J. 2007, 13, 923 – 935
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
933