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[D8]toluene, 25 °C): δ = –9.3 (10 B), 7.4 (2 B), –6.3 (4 B), –2.3 (4
B) ppm. EI-MS (70 eV): m/z (%) = 705 (2) [M – C3H7]+, 374 (20)
[M/2]+, 358 (5) [M/2 – CH4]+, 331 (20) [M/2 – C3H7]+, 43 (100).
for two months, after which transparent yellow crystals of 9(Se)
[m.p. 140–150 °C (dec.)] could be collected. The principle structure
of 9(Se) was confirmed by X-ray analysis, although severe disorder
in the region of the selenium atoms prevented an exact determi-
nation of a meaningful data set. The solution in [D8]toluene con-
tained 9, 9(Se), 23, bis(diselane) 24,[21] and several unidentified
products (from 31P and 77Se NMR spectroscopy).
22: 1H NMR (500.13 MHz, CD2Cl2, 25 °C): δ = 4.43 (s, 1 H,
CcarbH), 6.57 (d, 1J31P,1H = 477.3 Hz, 1 H, PH) ppm. 1H{31P} NMR
(500.13 MHz, CD2Cl2, 25 °C): δ = 4.43 (s, 1 H, CcarbH), 6.57 (s, 1
H, PH).
20: 1H{11B} NMR (500.13 MHz, CD2Cl2, 25 °C): δ = 1.22 [m, 2
H, C(4)Ha from PCy], 1.35 [m, 8 H, C(2)Ha and C(3)Ha from PCy],
1.71 [m, 2 H, C(4)Hb from PCy], 1.87 [m, 4 H, C(3)Hb from PCy],
2.13 [m, 6 H, C(2)Hb and PC(1)H from Cy], 2.21 [br. s, 2 H, HB
for δ(11B) = –9.0 ppm], 2.25 [br. s, 2 H, HB for δ(11B) = –7.3 ppm],
2.47 [br. s, 4 H, HB for δ(11B) = –2.4 ppm], 2.56 [br. s, 6 H, HB for
δ(11B) = –9.0 ppm], 2.70 [br. s, 4 H, HB for δ(11B) = –6.5,
–7.3 ppm], 2.99 [br. s, 2 H, HB for δ(11B) = –9.0 ppm] ppm.
11B{1H} NMR (160.5 MHz, CD2Cl2, 25 °C): δ = –9.0 (10 B), –7.3
(4 B), –6.6 (2 B), –2.4 (4 B) ppm.
2-Cyclohexyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3,2-disel-
enaphospholane (9): CyPCl2 (0.032 mL, 0.21 mmol) was added
through a microsyringe to a solution of 5 (75.5 mg, 0.211 mmol) in
CD2Cl2 (0.6 mL) at room temp. The progress of the reaction was
monitored by 31P and 29Si NMR spectroscopy. After 1 h at room
temp., the mixture contained 9 together with Me2SiCl2. The volatile
materials were removed under vacuum (3 h, 8ϫ 10–3 Torr) to give
1
9 as a white solid. H{11B} NMR (500.13 MHz, CD2Cl2, 25 °C): δ
3
31P,1H
= 1.07 [dm, J
= 8.3 Hz, 2 H, C(2)Ha], 1.22 [m, 1 H, C(4)Ha],
1.37 [m, 2 H, C(3)Ha], 1.71 [m, 1 H, C(4)Hb], 1.87 [m, 2 H, C(3)
Hb], 1.94 [m, 2 H, C(2)Hb], 2.28 [br. s, 2 H, HB for δ(11B) =
–6.5 ppm], 2.38 [br. s, 1 H, HB for δ(11B) = –6.5 ppm], 2.40 [br. s,
1 H, HB for δ(11B) = –3.8 ppm], 2.43 [br. s, 2 H, HB for δ(11B) =
–10.7 ppm], 2.57 [br. s, 2 H, HB for δ(11B) = –8.6 ppm], 2.73 [dtt,
9(Se): 1H{11B} NMR (500.13 MHz, [D8]toluene, 25 °C): δ = 0.82
[m, 1 H, C(4)Ha], 0.90 [m, 2 H, C(3)Ha], 1.31 [m, 3 H, C(2)Ha and
C(4)Hb], 1.49 [m, 2 H, C(3)Hb], 1.64 [m, 2 H, C(2)Hb], 2.60 [m,
3J1H,1H = 11.9 Hz, 1 H, PC(1)H], 2.61 [br. s, 4 H, HB for δ(11B)
= –9.0tpranps m], 2.75 [br. s, 3 H, HB for δ(11B) = –6.4, –4.2 ppm], 2.88
[br. s, 1 H, HB for δ(11B) = –5.3 ppm], 3.00 [br. s, 1 H, HB for
δ(11B) = –0.6 ppm], 3.50 [br. s, 1 H, HB for δ(11B) = –4.2 ppm]
ppm. 11B{1H} NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –9.0 (4
2J
= 3.5 Hz, 3J
= 12.2 Hz, 3J
31P,1H
1H,1Htrans
1H,1Hcis
= 3.6 Hz, 1 H,
PC(1)H], 2.78 [br. s, 1 H, HB for δ(11B) = –8.0 ppm], 3.01 [br. s, 1
H, HB for δ(11B) = 0.2 ppm] ppm. 11B{1H} NMR (160.5 MHz,
CD2Cl2, 25 °C): δ = –10.7 (2 B), –8.6 (2 B), –8.0 (1 B), –6.5 (3 B),
–3.8 (1 B), 0.2 (1 B) ppm. 11B NMR (160.5 MHz, CD2Cl2, 25 °C):
B), –6.4 (1 B), –5.3 (1 B), –4.2 (3 B), –0.6 (1 B) ppm. 11B NMR
1
1
1
11B,1H
(160.5 MHz, [D8]toluene, 25 °C): δ = –9.0 (d, J
= 180 Hz, 4
11B,1H
11B,1H
= 168 Hz, 2
δ = –10.7 (d, J
= 165 Hz, 2 B), –8.6 (d, J
1
1
1
1
11B,1H
11B,1H
= 155 Hz, 1 B), –5.3 (d, 1 B), –4.2 (d, J
B), –6.4 (d, J
11B,1H
11B,1H
= 153 Hz, 3 B), –3.8 (d, J
B), –8.0 (d, 1 B), –6.5 (d, J
= 157 Hz, 3 B), –0.6 (d, 1J
= 142 Hz, 1 B) ppm. EI-MS
= 148 Hz, 1 B), 0.2 (d, 1J11B,1H = 176 Hz, 1 B) ppm. 1H{11B} NMR
11B,1H
(70 eV): m/z (%) = 493 (5) [M]+, 414 (4) [M – Se]+, 379 (2), 331
3
31P,1H
(500.13 MHz, [D8]toluene, 25 °C): δ = 0.59 [dm, J
= 8.2 Hz,
(12) [M – Se – C6H11]+, 83 (100) [C6H11].
2 H, C(2)Ha], 0.86 [m, 1 H, C(4)Ha], 0.92 [m, 2 H, C(3)Ha], 1.37
[m, 1 H, C(4)Hb], 1.47 [m, 2 H, C(3)Hb], 1.56 [m, 2 H, C(2)Hb],
1
23: H NMR (500.13 MHz, [D8]toluene, 25 °C): δ = 4.23 (s, 1 H,
2
3
3
31P,1H
2.44 [dtt, J
= 2.9 Hz, J1H,1H
= 12.3, J1H,1H = 3.8 Hz, 1
trans cis
C
carbH), 5.79 (d, 1J31P,1H = 476.5 Hz, 1 H, PH) ppm. 1H{31P} NMR
H, PC(1)H], 2.59 [br. s, 2 H, HB for δ(11B) = –10.5 ppm], 2.73 [br.
s, 5 H, HB for δ(11B) = –6.0, –8.4 ppm], 2.77 [br. s, 2 H, HB for
δ(11B) = –3.3, –7.8 ppm], 3.14 [br. s, 1 H, HB for δ(11B) = 0.2 ppm]
ppm. 11B{1H} NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –10.5 (2
(500.13 MHz, [D8]toluene, 25 °C): δ = 4.23 (s, 1 H, CcarbH), 5.79
(s, 1 H, PH).
2-(1,1-Dimethylethyl)-4,5-[1,2-dicarba-closo-dodecaborano(12)]-
1,3,2-diselenaphospholane (10): A solution of 5 (92 mg, 0.257 mmol)
in [D8]toluene (0.4 mL) was cooled to –30 °C, and a solution of
tBuPCl2 (40.8 mg, 0.257 mmol) in [D8]toluene (0.2 mL) was added.
The progress of the reaction was monitored by 31P and 29Si NMR
spectroscopy. After 2 h at room temp., the mixture contained 10
(ca. 80 %) and a stereoisomeric mixture of oligomers (20%) to-
gether with Me2SiCl2. The volatile materials were removed under
vacuum (2 h, 8ϫ10–3 Torr) to give a white solid. One part of the
remaining solid was dissolved in [D8]THF. After 2 h at room temp.,
the mixture contained 10 (ca. 65%), 21 (30%), and 21Ј (possibly a
trimer, 5%). After 1 d at room temp., the mixture contained 10
(5%), 21 (90%), and 10(Se) (5%; Figure 5, A–C). A second part of
the remaining solid was dissolved in [D8]toluene, and the precipi-
tate was separated by centrifugation and redissolved in [D8]toluene;
the mixture contained 21 (70%) and 21Ј (possibly a trimer, 30%)
as determined by 31P NMR spectroscopy. After 20 h at room temp.,
the mixture contained 21 (90%), 21Ј (10%), and bis(diselane) 24
(from 31P and 77Se NMR spectroscopy; Figure 5, D–F).
B), –8.4 (2 B), –7.8 (1 B), –6.0 (3 B), –3.3 (1 B), 0.2 (1 B) ppm.
1
11B NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –10.5 (d, J
=
11B,1H
1
11B,1H
166 Hz, 2 B), –8.4 (d, J
= 164 Hz, 2 B), –7.8 (d, 1 B), –6.0
1
1
11B,1H
11B,1H
= 147 Hz, 1 B), 0.2 (d,
(d, J
= 150 Hz, 3 B), –3.3 (d, J
1J
= 180 Hz, 1 B) ppm. EI-MS (70 eV): m/z (%) = 415 (12)
11B,1H
[M]+, 332 (5) [M – C6H11]+, 83 (100).
2,7-Di(cyclohexyl)-4,5,9,10-bis[1,2-dicarba-closo-dodecaborano-
(12)]-2,7-diphospha-1,3,6,8-tetraselenacyclodecane (20): A solution
of 5 (100.9 mg, 0.28 mmol) in [D8]toluene (0.6 mL) was cooled to
–30 °C, and CyPCl2 (0.043 mL, 0.28 mmol) was added through a
microsyringe. The progress of the reaction was monitored by 31P
and 29Si NMR spectroscopy. After 30 min at room temp., the mix-
ture contained 9 together with Me2SiCl2. After 24 h at room temp.,
the mixture contained 9 (ca. 85%), 20 (10%), and 9(Se) (5%) to-
gether with Me2SiCl2. The volatile materials were removed under
vacuum (1 h, 8ϫ 10–3 Torr), and the residue was dissolved in [D8]-
toluene. This solution in [D8]toluene was kept for 1 week at –30 °C,
and the formation of 20 as a fairly insoluble white powder was
observed. The precipitate was separated by centrifugation, washed
with [D8]toluene, and dried under vacuum to give 20 as a light
yellowish solid; m.p. 165–175 °C (dec.). The dimer 20 was dissolved
in [D8]THF; after 1 h at room temp., the solution contained 9
(75%), 20 (20%), and 9(Se) (5%), and after 30 min at 50 °C, the
mixture contained 9 (80%), 9(Se) (15%), and 23 (5%; Figure 4).
The residual solution in [D8]toluene was left at room temperature
10: 1H NMR (500.13 MHz, [D8]toluene, 25 °C): δ = 0.81 (d, 3J
31P,1H
= 13.2 Hz, 9 H, CH3) ppm.
21: 1H NMR (500.13 MHz, [D8]toluene, 25 °C): δ = 0.98 (d, 3J
31P,1H
= 15.2 Hz, 18 H, CH3) ppm.
21Ј: 1H NMR (500.13 MHz, [D8]toluene, 25 °C): δ = 1.07 (d,
3J
= 15.2 Hz, 27 H, CH3) ppm.
31P,1H
Eur. J. Inorg. Chem. 2014, 1929–1948
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