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1
yield). 31P{1H} NMR (CDCl3): d(ppm) 26.2 (s, JP–Se = 697 Hz). 1H
NMR (CDCl3): d(ppm) 8.78 (br s, 3H), 7.94 (dd, JH–H = 20.8 Hz,
JH–H = 3.26 Hz, 9H), 7.47–7.33 (m, 9H). Anal. Calc. for C30H21PSe: C,
73.32; H, 4.31. Found: C, 73.12; H, 4.26%.
20 h. After cooling, the dark blue solution was filtered and the sol-
vent was removed in vacuo. The resulting orange solid was recrys-
tallized from Et2O in the freezer to yield clear, colorless crystals of
SiBuSB (0.1859 g, 34% yield). 31P{1H} NMR (CDCl3): d(ppm) 80.2 (s).
1H NMR (CDCl3): d(ppm) 2.97 (br s, 12H, bridging –CH2–), 2.80 (d,
JH–H = 2.23 Hz, 6H, iBu –CH2–), 2.30 (m, 3H, –CH–), 0.94
(d, JH–H = 2.67 Hz, 18H, –CH3). Anal. Calc. for C18H39N4PS: C,
57.72; H, 10.49. Found: C, 57.74; H, 10.62%.
2.2.3. dmpeSe2
dmpe (1.0 g, 6.7 mmol) and selenium (1.1437 g, 14.48 mmol)
were dissolved in toluene (20 mL) in a glovebox. The solution
was removed from the glovebox and refluxed for 44 h. The solution
was filtered and the solvent was removed in vacuo to yield a light
gray solid. The solid was triturated with Et2O (3 ꢂ 5 mL) to produce
light pink dmpeSe2 (0.060 g, 2.9%). 31P{1H} NMR (CDCl3): d(ppm)
2.2.9. SeiBuSB
In a glovebox, iBuSB (0.50 g, 1.5 mmol) and selenium (0.1154 g,
1.46 mmol) were dissolved in 20 mL toluene. The solution was
removed from the glovebox and heated at reflux under argon for
20 h. After cooling, the yellow solution was filtered and the solvent
was removed in vacuo. The solid was washed with Et2O (2 mL) to
yield a light pink solid. The solid was recrystallized through slow
evaporation at room temperature of the solvent, CH2Cl2, to yield
clear colorless crystals of SiBuSB (0.0427 g, 7.7% yield). 31P{1H}
21.8 (s, JP–Se = 706 Hz, JP–P = 60.7 Hz, JP–Se = 55.5 Hz). 1H NMR
(CDCl3): d(ppm) 2.30 (m, 4H, –CH2–), 1.96 (virtual triplet, 12H,
–CH3). Anal. Calc. for C6H16P2Se2: C, 23.39; H, 5.24. Found: C,
23.52; H, 5.60%.
1
3
4
2.2.4. dcpeS2
1
dcpe (0.4993 g, 1.181 mmol) and sulfur (0.0729 g, 2.27 mmol)
were heated at reflux in toluene (30 mL) for 16 h. Upon cooling
the colorless solution was filtered, and the solvent was removed
in vacuo. The resulting solid was triturated with Et2O (3 ꢂ 5 mL)
to give dcpeS2 as a white solid (0.514 g, 90% yield). 31P{1H} NMR
(CDCl3): d(ppm) 62.4 (s). 1H NMR (CDCl3): d(ppm) 1.84 (m, 44H,
–C6H11) 1.20 (m, 4H, –CH2–). Anal. Calc. for C26H48P2S2: C, 64.16;
H, 9.94. Found: C, 64.17; H, 9.98%.
NMR (CDCl3): d(ppm) 78.2 (s, JP–Se = 770 Hz). 1H NMR (CDCl3):
d(ppm) 2.97 (br s, 12H, bridging –CH2–), 2.80 (d, JH–H = 2.09 Hz,
i
6H, Bu –CH2–), 2.30 (m, 3H, –CH–), 0.96 (d, JH–H = 2.67 Hz, 18H,
–CH3). Anal. Calc. for C18H39N4PSe: C, 51.30; H, 9.33. Found: C,
51.32; H, 9.50%.
2.2.10. 2,3-dppbS2
2,3-dppb (0.1248 g, 0.2926 mmol) and sulfur (0.0218 g,
0.680 mmol) were stirred in toluene (10 mL) for 48 h. The solution
was filtered and the solvent was removed in vacuo. The resulting
solid was rinsed with Et2O (2 ꢂ 5 mL). The solid was recrystallized
twice from minimal CH2Cl2 and Et2O yielding clear, colorless crys-
tals (0.0360 g, 25% yield). 31P{1H} NMR (CDCl3): d(ppm) 80.2. 1H
NMR (CDCl3): d(ppm) 7.77 (m, 12H, –Ph), 7.45 (m, 8H, –Ph), 3.45
(m, 2H, –CH–), 1.27 (m, 6H, –CH3). Anal. Calc. for C28H28P2S2: C,
68.55; H, 5.75. Found: C, 68.20; H, 5.91%.
2.2.5. dcpeSe2
dcpe (0.6639 g, 1.569 mmol) and selenium (0.2510 g,
3.179 mmol) were heated at reflux in toluene (30 mL) for 16 h.
Upon cooling the light yellow solution was filtered, and the solu-
tion was dried in vacuo. The residue was triturated with Et2O
(3 ꢂ 5 mL) to give dcpeSe2 as a light orange solid (0.8570 g, 94%
yield). 31P{1H} NMR (CDCl3): d(ppm) 57.6 (s, JP–Se = 714 Hz,
1
3JP–P = 45.0 Hz, JP–Se = 17.3 Hz). 1H NMR (CDCl3): d(ppm) 1.85 (m,
4
44H, –C6H11), 1.25 (m, 4H, –CH2). Anal. Calc. for C26H48P2Se2: C,
2.2.11. 2,3-dppbSe2
53.79; H, 8.33. Found: C, 54.12; H, 8.43%.
2,3-dppb (0.1269 g, 0.2976 mmol) and selenium (0.0476 g,
0.603 mmol) were stirred in toluene (10 mL) for 24 h. The solution
was filtered and the solvent was removed in vacuo. The resulting
solid was rinsed with Et2O (3 ꢂ 5 mL). The solid was recrystallized
from minimal CH2Cl2 and Et2O, filtered, and rinsed with Et2O
(2 ꢂ 5 mL). The solid was dried in vacuo to give an initial crop
of product as a white solid (0.0076 g, 4.4% yield). A second crop
of product was obtained as clear, colorless crystals from the
supernatant through slow evaporation of CH2Cl2 (0.0292 g, 17% yield)
2.2.6. PhpleS2
Phple (0.0507 g, 0.100 mmol) and sulfur (0.0062 g, 0.19 mmol)
were heated at reflux in toluene (10 mL) for 1.5 h. The solution
was filtered and the solvent was removed in vacuo. The resulting
solid was triturated with Et2O (3 ꢂ 5 mL) to give white PhpleS2
(0.0294 g, 54% yield). 31P{1H} NMR (CDCl3): d(ppm) 71.0 (s). 1H
NMR (CDCl3): d(ppm) 7.34 (m, 8H, –Ph), 7.17 (m, 12H, –Ph), 3.54
(m, 2H, –CH–), 3.24 (m, 2H, –CH–), 2.35 (m, 4H, –CH2CH2–),
2.15–2.01 (m, 4H, –CH2–), 1.63 (m, 2H, –CH2–), 0.84 (m, 2H,
–CH2–). Anal. Calc. for C34H36P2S2: C, 71.55; H, 6.36. Found: C,
71.91; H, 6.28%.
for
a
21% total yield. 31P{1H} NMR (CDCl3): d(ppm) 48.7
1
3
4
(s, JP–Se = 735 Hz, JP–P = 62.4 Hz, JP–Se = 59.4). 1H NMR (CDCl3):
d(ppm) 7.82 (m, 12H, –Ph), 7.45 (m, 8H, –Ph), 3.69 (m, 2H, –CH–)
1.22 (m, 6H, –CH3). Anal. Calc. for C28H28P2Se2: C, 57.55; H, 4.83.
Found: C, 57.92; H, 4.65%.
2.2.7. PhpleSe2
Phple (0.0504 g, 0.0995 mmol) and selenium (0.0191 g,
0.241 mmol) were heated at reflux in toluene (10 mL) for 1.5 h.
The solution was filtered and the solvent was removed in vacuo.
The resulting solid was triturated with Et2O (3 ꢂ 5 mL) to give pink
PhpleSe2 (0.0573 g, 87% yield). 31P{1H} NMR (CDCl3): d(ppm) 63.4
(s, 1JP–Se = 737 Hz, 3JP–P = 43.3 Hz, 4JP–Se = 25.9 Hz). 1H NMR (CDCl3):
d(ppm) 7.36 (m, 8H, –Ph), 7.18 (m, 10H, –Ph), 3.76 (m, 2H, –CH–),
3.40 (m, 2H, –CH–), 2.34 (m, 4H, –CH2CH2–), 2.11 (m, 4H, –CH2–),
1.77 (m, 2H, –CH2–), 0.91 (m, 2H, –CH– Anal. Calc. for C34H36P2Se2:
C, 61.45; H, 5.46. Found: C, 61.09; H, 5.49%.
2.3. X-ray crystallography
Crystals of dppbS2, dpppentS2, dpppSe2, dppbzSe2, SeMeSB,
SiBuSB and SeiBuSB were obtained by vapor diffusion of Et2O into
a solution of the corresponding compound in CH2Cl2 (Table 3).
Crystals of 2,3-dppbS2 and 2,3-dppbSe2 were obtained by slow
evaporation of an Et2O solution of the compound (Table 3). X-ray
diffraction data were collected on a Bruker-AXS Kappa APEX II
CCD diffractometer with 0.71073 Å Mo K
a radiation. All of the
samples were mounted onto a glass fiber using Loctite Super Glue,
and data were collected at the reported temperatures. Cell param-
eters were found using APEX II software and refined using SAINT+ on
all observed reflections [51,52]. Unit cell parameters were obtained
from 60 data frames, 0.5° /, from three different sections of the
Ewald sphere. Each data set was treated with SADABS absorption
2.2.8. SiBuSB
In a glovebox, iBuSB (0.50 g, 1.5 mmol) and sulfur (0.0499 g,
1.53 mmol) were dissolved in 20 mL toluene. The solution was
removed from the glovebox and heated at reflux under argon for