1436
M. Granitzka et al. · The Bis-2-thienyldiethylaminophosphane Ligand
product distilled (oil bath at 60 – 70◦C). Cl2PNEt2 was ob- Synthesis of [(C4H3S)2PNEt2·CuCl/Br (CH3CN)]2 (4)
tained as a colorless liquid (72.2 g, 0.42 mol, 60.4 mL, 83%;
To copper(I)chloride (0.1 g, 10 mmol, 1.0 eq.) dissolved
Lit: 88% [62]). The purity of the product was confirmed
by NMR spectroscopy (31P: δ = 162.4 ppm). To a suspen-
in abs. acetronitrile (10 mL) 1 (0.27 g, 11.6 mmol, 1.16 eq.)
was added at room temperature, and the mixture was stirred
sion of magnesium turnings (16.7 g, 0.69 mol, 2.5 eq.) in thf
for 24 h. The reaction mixture was filtered through a glass
(80 mL) a few drops of 2-bromothiophene were added until
filter, and the filtrate was stored at −35◦C for 7 days. Yellow
the reaction started, and the rest (99.7 g, 0.61 mol, 57.3 mL,
crystals of 4 could be isolated (0.089 g, 20%). – 1H NMR
2.22 eq.) were added dropwise to maintain the reaction. Af-
3
(300.13 MHz, C6D6): δ = 0.96 (t, J = 7.0 Hz, 6 H, CH3),
ter the reaction was finished and cooled to room temper-
3.34 (dq, 3J = 14.0, 7.0 Hz, 4 H, CH2), 6.74 (ddd, 3J = 4.9,
3.6, 1.5 Hz, 2 H, 4-H), 7.07 (m, 2 H, 3-H), 7.82 ppm (ddd,
3J = 7.8, 3.5, 1.1, 2 H, 5-H). – 31P NMR (121.49, C6D6) :
δ = 30.5 ppm.
ature, the unreacted magnesium was filtered off. The fil-
trated was cooled to 0◦C, and Cl2PNEt2 (47.8 g, 0.28 mol,
40 mL, 1 eq.) was added dropwise within 1 h, and the mix-
ture was stirred for another hour. Pentane (200 mL) was
added, the precipitate was filtered off (P2 frit) and washed
with pentane (5 × 50 mL). The volume of the collected so-
lution was reduced, filtered (P4 frit with Celite) and washed
with pentane (3 × 15 mL) again. After removal of the sol-
vent, 1 could be obtained as a brownish liquid (41.3 g,
0.15 mol, 49.1 mL, 56%). C12H16NPS2 (M = 269.37). –
MS (EI, 70 eV): m/z = 269 [M]+, 197 [M–NEt2]+. – 1H
Synthesis of [{(C4H3S)2PNEt2}2·PdCl/Br2] (5)
To bis(benzonitrile)palladium(II) chloride (0.79 g.
2.06 mmol, 1 eq.) dissolved in toluene (25 mL) one equiva-
lent of 1 was added. Only a few crystals of the product could
be isolated.
3
Synthesis of [{(C4H3S)2PNEt2}·PdCl/Br2]2 (6)
NMR (300.13 MHz, C6D6): δ = 0.90 (t, J = 7.1 Hz, 6 H,
CH3), 3.08 (dq, 3J = 10.8, 7.1 Hz, 4 H, CH2), 6.81 (ddd,
3J = 4.8, 3.5, 1.3 Hz, 2 H, 4-H), 7.17 ppm (m, 4 H, 3-
H, 5-H). – 13C NMR (75.47 MHz, C6D6): δ = 14.59 (d,
3J = 3.8 Hz, CH3), 44.33 (d, 2J = 15.8 Hz, CH2), 127.96
A few crystals of 6 could be isolated, which were used
1
for analysis. – H NMR (300.13 MHz, C6D6): δ = 1.03 (t,
3J = 7.1 Hz, 6 H, CH3), 3.47 (m, 4 H, CH2), 6.75 (ddd, 3J =
4.6, 1.7, 0.9 Hz, 2 H, 4-H), 7.06 (m, 2 H, 3-H,), 7.93 ppm
(ddd, 3J = 6.8, 3.3, 1.1, 2 H, 5-H). – 31P NMR (121.49 MHz,
C6D6): δ = 49.70 ppm.
3
3
(d, J = 5.9 Hz, 4-C), 130.60 (d, J = 2.2 Hz, 5-C), 133.62
(d, 2J = 23.8 Hz, 3-C), 143.29 ppm (d, 1J = 30.3 Hz, 2-C). –
31P NMR (121.49 MHz, C6D6): δ = 38.69 ppm.
Synthesis of [(C4H3S)2PNEt2·IrCl/Br(C8H12)] (7)
General procedure for the synthesis of compounds 2–7
To bis(1,5-cyclooctadiene)diiridium(I) dichloride (10 mg,
1.5 × 10−2 mmol, 0.5 eq.) dissolved in toluene (5 mL) was
added one equivalent of 1 (8 mg, 0.03 mmol). A few crys-
tals of 7 could be isolated, which were used for anal-
ysis. – MS (EI, 70 eV): m/z = 649.0 [MBr]+, 605.0
[MCl]+, 577.0 [MBr–NEt2]+, 566.0 [MBr–Thi]+, 534.0
[MCl–NEt2]+, 496.0 [MCl–COD]+, 458.9 [MBr–COD–
Thi]+, 269.0 [Thi2PNEt2]+, 197.0 [Thi2P]+, 115.0 [PThi]+,
91.0 [Tol–H]+. – 31P NMR (121.49 MHz, C6D6): δ =
49.19 ppm.
The corresponding metal salt was dissolved in a dry sol-
vent, and 1 was added (details see below). After stirring for
24 h at room temperature the precipitate was filtered off, and
the remaining solution was placed in a freezer for crystal-
lization. Within a few days single crystals suitable for X-ray
experiments were obtained.
Synthesis of [{(C4H3S)2PNEt2}2·NiCl/Br2] (2)
To [NiCl2(diglyme)]2 (0.60 g, 1.4 mmol, 1.0 eq.) dis-
solved in toluene (15 mL) one equivalent of 1 was added.
After several days at −20◦C light-green crystals could be
isolated. – MS (EI, 70 eV): m/z = 442 [MBr/Cl–L]+, 362
[MCl–L–Cl]+, 329 [MCl–L–Cl2]+, 269 [Thi2PNEt2]+, 197
[Thi2P]+, 115 [PThi]+.
Synthesis of (C4H3S)2PCl (8) [30]
Through a solution of 1 (21.3 g, 79 mmol, 25.3 mL)
in pentane (500 mL) gaseous HCl was passed at 0◦C for
30 – 45 min. The precipitated Et2NH·HCl was filtered off
and washed with pentane (3 × 20 mL). The solvents were re-
moved under reduced pressure, and the product was obtained
as slightly yellow crystals (18.0 g, 77.5 mmol, 98%). – 1H
Synthesis of [(C4H3S)2PNEt2·AuCl/Br] (3)
(Me2S)AuCl (0.05 g, 0.17 mmol, 1.0 eq.) was dissolved NMR (300.13 MHz, C6D6): δ = 6.58 (ddd, 3J = 5.0, 3.6 Hz,
in toluene (30 mL), and 1 (0.05 g, 0.21 mmol, 1.2 eq.) was 4J = 1.6 Hz, 2 H, 4-H), 7.04 (dd, 3J = 4.9, 4J = 1.1 Hz, 2 H,
added. After several days at −20◦C only a few yellow crys- 5-H), 7.25 ppm (ddd, 3J = 6.7, 3.5, 4J = 1.1 Hz, 2 H, 3-H).
tals could be isolated.
–
31P NMR (121.49 MHz, C6D6): δ = 53.36 ppm.
Brought to you by | Michigan State University
Authenticated
Download Date | 6/9/15 6:21 PM