Journal of the American Chemical Society
Article
Ph2P), 2.14 (d, 4JPH = 3.3 Hz, 3H, Me), 1.78 (s, 30H, C5Me5), 0.34 (d,
(d, 1JPC = 44.8 Hz, =CP), 124.6 (br m, CH), 121.9, 121.5 (C5Me5),
2
1
3
4JPH = 0.4 Hz, JSiH = 6.4 Hz, 9H, SiMe3). 13C{1H} NMR (126 MHz,
82.7 (d, JPC = 54.9 Hz, OCH), 28.4 (d, JPC = 36.0 Hz, Me), 12.6,
11.5 (C5Me5), 2.9 (d, JPSi = 2.2 Hz, SiMe3). 31P{1H} NMR (243
3
CD2Cl2, 299 K): δ = 267.1 (d, 2JPC = 13.2 Hz, ZrC), 148.5 (dm, 1JFC
∼
MHz, CD2Cl2, 299 K): δ = 18.3 (ν1/2 ∼ 2 Hz). 19F NMR (564 MHz,
CD2Cl2, 299 K): δ = −133.1 (br m, 2F, o-C6F5), −163.8 (t, 3JFF = 20.3
Hz, 1F, p-C6F5), −167.7 (br m, 2F, m-C6F5), [Δδ19Fmp = 3.9].
11B{1H} NMR (192 MHz, CD2Cl2, 299 K): δ = −16.7 (ν1/2 ∼ 25 Hz).
29Si(dept) NMR (99 MHz, CD2Cl2, 299 K): δ = −6.9 (d, 2JPSi = 23.6
Hz).
240 Hz, C6F5), 140.6 (d, 1JPC = 67.7 Hz, =CP), 138.6 (dm, 1JFC ∼ 245
1
4
Hz, C6F5), 136.6 (dm, JFC ∼ 245 Hz, C6F5), 134.2 (d, JPC = 2.7 Hz,
p-Ph2P), 133.2 (d, 2JPC = 10.3 Hz, o-Ph2P), 131.6 (d, 1JPC = 98.3 Hz, i-
Ph2P), 129.4 (d, 3JPC = 11.8 Hz, m-Ph2P), 125.7 (C5Me5), 124.2 (br, i-
3
3
C6F5), 27.9 (d, JPC = 41.5 Hz, Me), 12.1 (C5Me5), 1.9 (d, JPC = 3.4
Hz, SiMe3). 31P{1H} NMR (202 MHz, CD2Cl2, 299 K): δ = 49.1 (ν1/2
∼ 2 Hz). 19F NMR (470 MHz, CD2Cl2, 299 K): δ = −133.1 (br m, 2F,
o-C6F5), −163.9 (t, 3JFF = 20.3 Hz, 1F, p-C6F5), −167.7 (br m, 2F, m-
C6F5), [Δδ19Fmp = 3.8]. 11B{1H} NMR (160 MHz, CD2Cl2, 299 K): δ
= −16.7 (ν1/2 ∼ 25 Hz). 29Si(dept) NMR (99 MHz, CD2Cl2, 299 K):
Preparation of Compound 9. CH2Cl2 (2 mL) was added to a
mixture of complex 4a (67 mg, 0.05 mmol) and paraformaldehyde (ca.
2 mg, 0.07 mmol). Then the reaction mixture was stirred at room
temperature for 2 h. After filtration, cyclopentane (4 mL) was layered
to the filtrate to give a beige oil, which was separated and washed with
pentane (3 × 2 mL) to eventually give compound 9 as a pale yellow oil
(60 mg, 88%). Anal. Calcd for C63H54BF20OPSiZr. C5H10: C, 56.78;
2
δ = −12.9 (d, JPSi = 33.2 Hz).
Preparation of Compound 8a. Cinnamaldehyde (7 mg, 0.05
mmol) was added to a suspension of complex 4a (67 mg, 0.05 mmol)
in CH2Cl2 (2 mL), and then the reaction mixture was stirred for 2 h at
room temperature. After filtration, the filtrate was covered with
cyclopentane (4 mL) and the mixture was stored in the fridge (ca. −35
°C) for several days. Complex 8a was obtained as a pale yellow
crystalline solid (62 mg, 84%). Crystals suitable for the X-ray crystal
structure analysis were grown from a two-layer procedure using a
CH2Cl2 solution of compound 8a and cyclopentane at −35 °C. Anal.
Calcd for C71H60BF20OPSiZr. CH2Cl2: C, 55.60; H, 4.02. Found: C,
1
H, 4.49. Found: C, 56.94; H, 4.36. H NMR (600 MHz, CD2Cl2, 299
K): δ = 7.79 (m, 2H, p-Ph2P), 7.70 (m, 8H, o, m-Ph2P), 5.11 (d, 2JPH
=
4
0.8 Hz, 2H, OCH2), 2.08 (d, JPH = 3.2 Hz, 3H, Me), 1.81 (s, 30H,
2
C5Me5), 0.10 (s, JSiH = 6.4 Hz, 9H, SiMe3). 13C{1H} NMR (151
MHz, CD2Cl2, 299 K): δ = 269.7 (d, 2JPC = 25.3 Hz, ZrC), 148.5 (dm,
1
1JFC ∼ 245 Hz, C6F5), 138.6 (dm, JFC ∼ 245 Hz, C6F5), 136.7 (dm,
1JFC ∼ 240 Hz, C6F5), 134.7 (d, 4JPC = 2.9 Hz, p-Ph2P), 133.7 (d, 2JPC
3
= 8.7 Hz), 130.5 (d, JPC = 11.3 Hz)(o,m-Ph2P), 124.2 (br, i-C6F5),
1
56.45; H, 4.00. H NMR (600 MHz, CD2Cl2, 299 K): δ = 7.92 (2H,
122.8 (C5Me5), 122.3 (d, 1JPC = 76.6 Hz, i-Ph2P), 122.2 (d, 1JPC = 50.2
o), 7.81 (1H, p), 7.68 (2H, m) (each m, PhP), 7.78 (1H, p), 7.70 (2H,
o), 7.68 (2H, m) (each m, PhP), 7.34 (2H, m), 7.31 (1H, p), 7.24 (2H,
o) (each m, Ph), 6.40 (ddd, 3JHH = 15.9 Hz, J = 5.2 Hz, J = 2.2 Hz, 1H,
PhCH=), 6.03 (ddd, 3JHH = 15.9 Hz, J = 4.2 Hz, J = 2.6 Hz, 1H, =CH),
5.84 (m, 1H, OCH), 2.13 (d, 4JPH = 3.0 Hz, 3H, Me), 2.01, 1.70 (each
1
3
Hz, =CP), 68.8 (d, JPC = 60.1 Hz, OCH2), 27.8 (d, JPC = 37.3 Hz,
Me), 11.9 (C5Me5), 2.6 (d, 3JPC = 2.5 Hz, SiMe3). 31P{1H} NMR (243
MHz, CD2Cl2, 299 K): δ = 18.3 (ν1/2 ∼ 2 Hz). 19F NMR (564 MHz,
CD2Cl2, 299 K): δ = −133.1 (br m, 2F, o-C6F5), −163.9 (t, 3JFF = 20.3
Hz, 1F, p-C6F5), −167.7 (br m, 2F, m-C6F5), [Δδ19Fmp = 3.8].
11B{1H} NMR (192 MHz, CD2Cl2, 299 K): δ = −16.7 (ν1/2 ∼ 25 Hz).
29Si(dept) NMR (119 MHz, CD2Cl2, 299 K): δ = −8.1 (d, 2JPSi = 25.9
Hz).
Preparation of Compound 10. Following the procedure
described for the preparation of compound 8a, reaction of complex
4a (107 mg, 0.08 mmol) with PhNO (9 mg, 0.08 mmol) gave
compound 10 as a pale yellow solid (78 mg, 67%). Crystals suitable for
the X-ray crystal structure analysis were grown from a two-layer
procedure using a CH2Cl2 solution of compound 10 and cyclopentane
at −35 °C. Anal. Calcd for C68H57BF20NOPSiZr: C, 56.51; H, 3.98; N,
0.97. Found: C, 56.20; H, 4.13; N, 0.85. 1H NMR (600 MHz, CD2Cl2,
299 K): δ = 7.83 (m, 2H, p-Ph2P), 7.64 (br m, 8H, o,m-Ph2P), 7.11 (br
m, 2H, m-PhN), 7.08 (m, 1H, p-PhN), 6.47 (br, 2H, o-PhN), 2.19 (d,
4JPC = 3.4 Hz, 3H, Me), 1.80 (s, 30H, C5Me5), 0.06 (br, 9H, SiMe3).
13C{1H} NMR (151 MHz, CD2Cl2, 299 K): δ = 265.8 (d, 2JPC = 12.8
Hz, ZrC), 148.5 (dm, 1JFC ∼ 250 Hz, C6F5), 146.5 (d, 2JPC = 4.0 Hz, i-
2
s, each 15H, C5Me5), 0.06 (s, JSiH = 6.4 Hz, 9H, SiMe3). 13C{1H}
NMR (151 MHz, CD2Cl2, 299 K): δ = 267.3 (ZrC)1, 148.5 (dm, 1JFC
1
1
∼ 245 Hz), 137.8 (dm, JFC ∼ 245 Hz), 136.7 (dm, JFC ∼ 245 Hz),
124.5 (br) (C6F5), 136.0 (d, 2JPC = 7.2 Hz, o), 135.2 (d, 4JPC = 2.9 Hz,
p), 130.1 (d, JPC = 10.9 Hz, m)t, 124.4 (d, JPC = 75.5 Hz, i)t(PhP),
3
1
4
5
135.8 (d, JPC = 3.5 Hz, i), 129.3 (m), 129.1 (p), 127.0 (d, JPC = 1.6
4
2
Hz, o)(Ph), 134.3 (d, JPC = 3.0 Hz, p), 132.4 (d, JPC = 8.7 Hz, o),
130.7 (d, 3JPC = 11.2 Hz, m)t, 120.6 (d, 1JPC = 70.1 Hz, i)t(PhP), 134.5
(d, 3JPC = 10.7 Hz, PhCH), 124.7 (br, CH), 124.3 (d, 1JPC = 45.8
Hz, =CP), 123.1, 122.9 (C5Me5), 82.9 (d, 1JPC = 55.3 Hz, OCH), 27.4
3
3
(d, JPC = 36.5 Hz, Me), 12.5, 11.5 (C5Me5), 2.7 (d, JPC = 2.2 Hz,
SiMe3), [1 from the H,13C ghmbc experiment. tentatively assigned].
31P{1H} NMR (243 MHz, CD2Cl2, 299 K): δ = 15.7 (ν1/2 ∼ 2 Hz).
19F NMR (564 MHz, CD2Cl2, 299 K): δ = −133.1 (br m, 2F, o-C6F5),
1
t
3
−163.9 (t, JFF = 20.3 Hz, 1F, p-C6F5), −167.7 (br m, 2F, m-C6F5),
[Δδ19Fmp = 3.8]. 11B{1H} NMR (192 MHz, CD2Cl2, 299 K): δ =
−16.7 (ν1/2 ∼ 25 Hz). 29Si(dept) NMR (99 MHz, CD2Cl2, 299 K): δ
1
1
PhN)t, 138.6 (dm, JFC ∼ 250 Hz, C6F5), 136.6 (dm, JFC ∼ 245 Hz,
2
= −7.5 (d, JPSi = 24.2 Hz).
4
2
C6F5), 135.5 (d, JPC = 2.6 Hz, p-Ph2P), 135.1 (br d, JPC = 9.2 Hz),
Preparation of Compound 8b. Following the procedure
described for the preparation of compound 8a, reaction of complex
4c (71 mg, 0.05 mmol) with cinnamaldehyde (7 mg, 0.05 mmol) gave
compound 8b as a pale yellow crystalline solid (61 mg, 78%). Crystals
suitable for the X-ray crystal structure analysis were grown from a two-
layer procedure using a CH2Cl2 solution of compound 8b and
cyclopentane at −35 °C. Anal. Calcd for C71H60BF20OPSiHf: C, 54.75;
130.1 (d, 3JPC = 12.0 Hz)(o,m-Ph2P), 129.0 (br, m-PhN), 127.0 (d, 1JPC
= 71.8 Hz, =CP), 125.6 (p-PhN), 124.6 (d, JPC = 86.4 Hz, i-Ph2P)t,
1
123.6 (C5Me5), 120.8 (br, o-PhN)t, 27.4 (d, 3JPC = 38.2 Hz, Me), 12.0
3
(C5Me5), 2.7 (d, JPC = 3.7 Hz, SiMe3), n.o. (i-C6F5), [t tentative
assignment]. 31P{1H} NMR (243 MHz, CD2Cl2, 299 K): δ = 35.3
(ν1/2 ∼ 2 Hz). 19F NMR (564 MHz, CD2Cl2, 299 K): δ = −133.1 (br
m, 2F, o-C6F5), −163.9 (t, 3JFF = 20.1 Hz, 1F, p-C6F5), −167.7 (br m,
2F, m-C6F5), [Δδ19Fmp = 3.8]. 11B{1H} NMR (192 MHz, CD2Cl2, 299
K): δ = −16.7 (ν1/2 ∼ 20 Hz). 29Si(dept) NMR (99 MHz, CD2Cl2,
1
H, 3.88. Found: C, 53.83; H, 3.99. H NMR (600 MHz, CD2Cl2, 299
K): δ = 7.92 (2H, o), 7.81 (1H, p), 7.68 (2H, m) (each m, PhP), 7.78
(1H, p), 7.70 (2H, o), 7.69 (2H, m) (each m, PhP), 7.34 (2H, m), 7.31
(1H, p), 7.24 (2H, o)(each m, Ph), 6.40 (ddd, 3JHH = 15.8 Hz, J = 5.1
Hz, J = 2.2 Hz, 1H, PhCH), 6.02 (ddd, 3JHH = 15.8 Hz, J = 4.2 Hz, J
= 2.7 Hz, 1H, CH), 5.79 (m, 1H, OCH), 2.14 (d, 4JPH = 2.8 Hz, 3H,
Me), 2.06, 1.75 (each s, each 15H, C5Me5), 0.07 (s, 2JSiH = 6.4 Hz, 9H,
SiMe3). 13C{1H} NMR (151 MHz, CD2Cl2, 299 K): δ = 270.7 (d, 2JPC
2
299 K): −8.6 (d, JPSi = 39.4 Hz).
Preparation of Compound 11. A suspension of complex 4c (143
mg, 0.1 mmol) in C6H5Br (2 mL) was degassed and CO2 (1.5 bar)
was introduced to the evacuated reaction flask for 1 h. Then the
reaction mixture was covered with cyclopentane (4 mL) to eventually
give complex 11 as a white solid (119 mg, 81%). Anal. Calcd for
C63H52BF20O2PSiHf: C, 51.49; H, 3.57. Found: C, 51.31; H, 3.57. IR
(KBr): 1690 (CO) cm−1. 1H NMR (500 MHz, CD2Cl2, 299 K): δ =
7.95 (m, 4H, o-Ph2P), 7.83 (m, 2H, p-Ph2P), 7.72 (m, 4H, m-Ph2P),
1
1
= 23.6 Hz, ZrC), 148.5 (dm, JFC ∼ 245 Hz), 138.7 (dm, JFC ∼ 245
1
2
Hz), 136.7 (dm, JFC ∼ 245 Hz), 124.5 (br) (C6F5), 136.0 (d, JPC
7.1 Hz, o), 135.2 (d, JPC = 2.9 Hz, p), 130.7 (d, JPC = 11.3 Hz, m),
124.4 (d, JPC = 75.1 Hz, i) (PhP), 135.7 (d, JPC = 3.3 Hz, i), 129.3
(m), 129.1 (p), 127.0 (d, JPC = 1.8 Hz, o)(Ph), 134.3 (d, JPC = 2.8
Hz, p), 132.4 (d, 2JPC = 8.8 Hz, o), 130.0 (d, 3JPC = 10.8 Hz, m), 120.6
(d, 1JPC = 70.5 Hz, i)(PhP), 134.5 (d, 3JPC = 9.9 Hz, PhCH), 125.3
=
4
3
1
4
1.88 (s, 30H, C5Me5), 1.87 (d, 4JPH = 3.1 Hz, 3H, Me), 0.17 (s, 2JSiH
6.4 Hz, 9H, SiMe3). 13C{1H} NMR (126 MHz, CD2Cl2, 299 K): δ =
=
5
4
2
1
273.9 (d, JPC = 22.4 Hz, HfC), 164.3 (d, JPC = 103.2 Hz, CO),
12440
dx.doi.org/10.1021/ja5068146 | J. Am. Chem. Soc. 2014, 136, 12431−12443