486
H. Braunschweig and M. Koster · Synthesis and Reactivity of Diborane(4)yl Complexes
1H NMR (125.697 MHz): 13C 1H NMR: = 34.36, 39.01, 42.63, 47.97 (NMe2),
(BBr), 62.7 (BW). – 13
C
=
39.32, 41.30, 41.93, 43.08 (NMe2), 92.40 (C5H5), 216.17, 54.09 (OMe), 92.64 (C5H5), 226.07, 226.71, 234.14
219.23, 222.77 (CO). – C12H17B2BrWN2O3 (522.65): (CO).– C13H20B2MoN2O4 (385.87): calcd. C 40.46, H
calcd. C 27.58, H 3.28, N 5.36; found C 27.12, H 3.24, N 5.22, N 7.26; found C 40.51, H 5.01, N 7.18.
4.87.
12: As described for 10, 0.54 g (1.68 mmol) of 1 [4]
8: As described for 5, 2.13 g (5.53 mmol) of is dissolved in 20 ml of ethanol to give an insepara-
K[ 5-(C5H4Me)W(CO)3 ] [9] is treated with 1.49 g ble, solid mixture of 12 and [ 5-(C5H5)Fe(CO)2 2]. –
3
(5.53 mmol) of B2(NMe2)2Br2 [11] to give 0.37 g (12.5%) 1H NMR: = 1.19 (t, J = 6.71 Hz, 3 H, OCH2CH3),
of 8 as a yellow solid. – IR (hexane): = 1987, 1907, 1889 2.46, 2.70, 2.89, 2.92 (4s, 12 H, NMe2), 3.73 (q,
(CO) cm 1. – 1H NMR: = 1.77 (s, 3H, C5H4Me), 2.47, 3J = 6.71 Hz, 2 H, OCH2CH3) 4.43 (s, 5 H, C5H5).
2.61, 2.66, 2.89 (4s, 12 H, NMe2), 5.00 (m, 4 H, C5H4Me).
11B NMR: = 40.0 (BBr), 63.2 (BW). – 13 1H NMR: NMR:
= 13.88 (C5H4Me), 39.38, 41.99, 43.10, 48.08 (NMe2), 48.60 (NMe2), 61.52 (OCH2CH3), 85.14 (C5H5), 218.13,
90.80, 91.12, 93.30, 93.57, 110.93 (C 5H4Me), 216.81, 218.24 (CO).
–
11B NMR: = 34.0 (BO), 69.1 (BFe). – 13C 1H
–
C
= 18.48 (OCH2CH3), 34.28, 38.93, 44.68,
219.95, 233.73 (CO). – C13H19B2BrWN2O3 (536.68):
13: As described for 10, 0.50 g (1.15 mmol) of 4 [5] is
calcd. C 29.09, H 3.57, N 5.22; found C 28.62, H 3.61, N dissolved in 20 ml of ethanol to give an inseparable, solid
1
5.03.
9: As described for 5, 1.97 g (5.30 mmol) of K[
mixture of 12 and [ 5-(C5H5)MoH(CO)3]. – H-NMR:
5
3
-
= 1.20 (t, J = 6.86 Hz, 3 H, OCH2CH3), 2.51, 2.62,
3
(C5H5)W(CO)3 ] [9] is treated with 1.23 g (5.30 mmol) 2.71, 2.88 (4s, 12 H, NMe2), 3.82 (q, J = 6.86 Hz, 2
of B2 (NC4H8)2Cl2 [6, 12] to give 0.23 g (8.1%) of 9 H, OCH2CH3)) 5.68 (s, 5 H, C5H5). – 11B NMR:
=
as a yellow solid. – IR (toluene): = 1985, 1900, 1884 33.4 (BO), 67.3 (BMo). - 13C 1H NMR: = 18.33
(CO) cm 1. - H NMR: = 1.79 (m, 8 H, NCH2CH2), (OCH2CH3), 34.46, 39.00, 42.66, 48.13 (NMe2), 61.88
1
3.28 (m, 8 H, NCH2CH2), 5.02 (s, 5 H, C5H5). – 11B (OCH2CH3), 93.93 (C5H5), 226.04, 226.87, 234.18 (CO).
NMR: = 39.6 (BCl), 60.2 (BW). – 13C 1H NMR:
14: 0.64 g (1.48 mmol) of 4 is dissolved in 90 ml of hex-
= 25.46, 25.76, 26.36, 26.75 (NCH2CH2), 47.15, 49.84, ane and 0.52 g (4.44 mmol) of PEt3 is added. The resulting
51.63, 55.76 (NCH2CH2), 92.37 (C5H5), 216.71, 218.77, mixture is irridiated for 15 h at –20 C with a Heraeus
222.90 (CO). – C16H21B2ClN2O3W(530.28): calcd. C
36.24, H 3.99, N 5.28; found C 35.89, H 4.18, N 5.01.
TQ 150 high pressure mercury lamp. The solution is fil-
tered, concentrated to 10 ml in high vacuum and stored
10: 0.30 g (0.93 mmol) of 1 [4] is dissolved in 20 ml at –30 C. 0.58 g (74.7%) of 14 is obtained as a yellow
of methanol and stirred for 1 h at ambient temperature. solid. – IR (toluene): = 1932, 1885, 1853, 1812 (CO)
1
3
All volatiles are removed under high vacuum, and the cm 1. – H NMR: = 0.82 (dt, JHH = 7.60 Hz, 3JPH
=
3
residue is treated with of 40 ml of hexane. After filtration 15.30 Hz, 9 H, PCH2CH3), 1.41 (dq, JHH = 7.60 Hz,
0.22 g (74.4%) of 10 is obtained at –30 C as a yel- 2JPH = 7.60 Hz, 6 H, PCH2CH3), 2.70, 2.81, 2.97, 3.08
low solid. – IR (hexane): = 1980, 1921 (CO) cm 1. – (4s, 12 H, NMe2), 5.10 (s (broad), 5 H, C5H5). - 11B NMR:
1H NMR: = 2.45, 2.68, 2.87, 2.92 (4s, 12 H, NMe2),
= 40.7 (BBr), 68.8 (BMo). – 13C 1H NMR: = 7.94
3.46 (s, 3 H, OMe) 4.41 (s, 5 H, C5H5). – 11B NMR: (d, J = 2.20 Hz, PCH2CH3), 22.12 (d, J = 26.30 Hz,
2
3
= 34.4 (BO), 69.0 (BFe). – 13 1H NMR: = 34.17, PCH2CH3), 39.32, 42.25, 42.96, 48.46 (NMe2), 92.32
C
2
2
38.94, 44.52, 48.41 (NMe2), 53.65 (OMe), 85.14 (C5H5), (C5H5), 231.70 (d, J = 21.40 Hz, CO), 224.30 (d, J =
218.06, 218.15 (CO). – C12H20B2FeN2O3 (317.77): calcd. 21.90 Hz, CO). – 31P 1H (202.34 MHz): = 52.8 (s). –
C 45.36, H 6.34, N 8.82; found C 44.98, H 6.24, N 8.37. C17H32B2BrMoN2O2P (524.89): calcd. C 38.90, H 6.14,
11: As described for 10, 0.38 g (0.87 mmol) of 4 [5] is N 5.34; found C 38.56, H 6.20, N 5.06.
dissolved in 20 ml of methanol to give 0.23 g (68.0 %) of
11 at –30 C as a yellow solid. – IR (hexane): = 1981,
1898, 1882 (CO) cm 1. – 1H NMR: = 2.50, 2.60, 2.70,
2.87 (4s, 12 H, NMe2), 3.52 (s, 3 H, OMe) 5.01 (s, 5
H, C5H5). – 11B NMR: = 33.7 (BO), 67.1 (BMo). –
Acknowledgements
HB thanks DFG, FCI, RSoc and EPSRC for financial
support.
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Download Date | 12/6/18 2:09 PM