Dalton Transactions
Paper
m/p-P(C
6
H
5
)
2
), 7.17–7.22 (m, 4H, o-P(C
6
H
5
)
2
), 7.39–7.46 (m, 3H, CH
2
P), 7.20–7.25 (m, 3H, m/p-SiC
6
H
5
), 7.70–7.74 (m, 2H,
1
3
1
13
1
m/p-SiC H ), 7.52–7.58 (m, 2H, o-SiC H ).
C{ H}-NMR: o-SiC H ). C{ H}-NMR: δ −0.6 (s, SiC ̲H ), 1.1 (d J 12.5 Hz,
3 PC
6
5
6
5
6
5
C
δ
C
−0.6 (s, SiC
uCCH P), 104.9 (d, JPC 4 Hz, CuC
Hz, m-C H ), 129.0 (s, p-C H ), 129.5 (s, p-C H ), 133.2 (d, p-C H ), 134.2 (s, o-C H ), 137.7 (s, i-C H ). P{ H}-NMR:
̲H
3
), 19.9 (d, JPC 21 Hz, C
̲
2
P), 85.7 (d, JPC 5 Hz, P{SiC
̲
3
}
2
), 5.5 (d, JPC 23 Hz, C
̲
2
P), 83.3 (d, JPC 4 Hz,
C̲
2
̲
2
P), 128.7 (d, JPC 6.5 vCCH
C
̲
2
P), 109.3 (br., CuCCH P), 128.2 (s, m-C
̲
2
6 5
H
), 129.6 (s,
3
1
1
6
5
6
5
6
5
6
5
6
5
6
5
2
9
1
JPC 19.5 Hz, o-C
6
H
5
), 134.2 (s, o-C
6
H
5
), 137.7 (s, i-C
6
H
5
),
δ
P
−84.4 (s, 5%), −158.9 (s, 14, 93%), −252.0 (s, 2%). Si{ H}-
Ph), 3.42 (P(SiMe ). Anal. Found: C,
3
1
1
1
38.1 (d, JPC 16 Hz, i-C
6
H
5
). P{ H}-NMR: δ −13.5 (s). NMR: δSi −23.0 (SiMe
P
2
3 2
)
2
9
1
Si{ H}-NMR: δ −22.9. Anal. Found: C, 76.89; H, 6.34. Calcd 58.29; H, 8.86. Calcd for C H PSi : C, 58.23; H, 8.91.
Si
17 31
3
for C23
H
23PSi: C, 77.06; H, 6.47.
{(Et
2
N)
2
P}C(Ph)vCvCH
2
(15). To
a
THF suspension
i
3
Pr SiCuCCH PPh (11). As for 8, using HPPh (0.780 g, (ca. 30 cm ) of excess, pre-activated magnesium turnings
3 2 2 2
−3
n
3
−3
−4
4
(
.24 × 10 mol), BuLi (2.5 M, 1.7 cm , 4.24 × 10 mol) and 4 containing HgCl (0.100 g, 3.68 × 10 mol) as initiator, was
2
0.976 g, 4.24 × 10− mol). Isolated as orange oil. Yield: 1.45 g, added drop-wise PhCuCCH Cl (1.00 g, 6.65 × 10−3 mol) as
3
2
1
3
9
6 6 H
0%. NMR (C D , 30 °C): H-NMR: δ 1.01 (m, 3H, SiCH), 1.09 solution in THF (ca. 10 cm ); upon complete addition the
3
(d, JHH 6.8 Hz, 18H, CH ), 2.75 (d, J 2.3 Hz, 2H, CH P), mixture was brought to reflux for 4 h. After allowing to cool to
3 PH 2
7
.02–7.12 (m, 6H, m/p-P(C
6
H
5
)
2
), 7.39–7.47 (m, 4H, o-P(C
6
H
5
)
2
). ambient temperature, the mixture was filtered (via cannula)
N) PCl
1
3
1
1
C{ H}-NMR: δ
C
11.7 (s, SiC
̲
2
2
3
−3
C
1
1
̲
H ), 19.9 (d, J 19.5 Hz, C
̲
̲
3
PC
PC
2
04.7 (d, JPC 4 Hz, CuC
̲
2
P), 128.7 (d, JPC 6.5 Hz, m-C
6
H
5
), stirred for 30 minutes at this temperature, before allowing it to
29.0 (s, p-C ), 133.1 (d, JPC 19 Hz, o-C
6
H
5
6
H
5
), 138.3 (d, JPC 16 attain ambient temperature and stir overnight. The resulting
3
1
1
29
1
Hz, i-C H ). P{ H}-NMR: δ −13.5 (s, JSiP 20 Hz). Si{ H}- orange solution was stripped of volatiles under reduced
6
5
P
NMR: δSi −3.03. Anal. Found: C, 75.77; H, 8.64. Calcd for pressure then extracted with pentane; this fraction was taken
33PSi: C, 75.74; H, 8.74. to dryness and dried in vacuo to afford the product as dark red
24
C H
n
1
Pr SiCuCCH PPh (12). As for 8, using HPPh (0.650 g, oil. Yield: 1.46 g, 76%. 15 (74%): NMR (C D , 30 °C): H-NMR:
3
2
2
2
6 6
−
3
n
3
−3
3
3
3
(
.49 × 10 mol), BuLi (2.5 M, 1.4 cm , 3.49 × 10 mol) and 5
δ
H
0.89 (t, JHH 7.0 Hz, 12H, CH
3
), 3.05 (q, JHH 7.0 Hz, 8H,
), 4.69 (d, JPH 7.0 Hz, 2H, vCH ), 7.11–7.15 (m, 3H, m/p-
0.805 g, 3.49 × 10− mol). Isolated as brown oil. Yield: 1.00 g, CH
3
2
2
1
13
1
8
0
0%. NMR (C D , 30 °C): H-NMR: δH 0.58 (m, 6H, SiCH2), C H ), 7.63–7.59 (m, 2H, o-C H ). C{ H}-NMR: δC 14.8 (d,
6
6
6
5
6 5
3
3
3
.99 (t, JHH 7.0 Hz, 9H, CH
3
), 1.42 (m, 6H, CH
2
CH
2
Si), 2.75 (d,
), 105.9 (d, JPC 13.5 Hz, i-C
.40–7.46 (m, 4H, o-P(C H ) ). C{ H}-NMR: δ 16.7 (s, C ̲H Si, {P(NEt ) }vC), 127.8 (s, o-C H ), 127.9 (overlapped m-/p-C H ),
6 5 2 C 2
J
PC 3.2 Hz, C
̲
3
), 43.4 (d, JPC 17.4 Hz, NC
2 2
̲H ), 75.0 (s, vC ̲H ),
), 137.4 (d, JPC 19 Hz, PhC̲-
JPH 2.5 Hz, 2H, CH
2
P), 7.04–7.12 (m, 6H, m/p-P(C
6
H
5
)
2
6
H
5
1
3
1
7
2 2
6
5
6
5
1
2
31
1
J
SiC 56 Hz,), 18.0 (s, C
̲
3
), 18.5 (s, C
̲
2
CH
vCCH
CH P), 128.5 (d, J 6.6 Hz, m-C H ), 129.0 (s, δH 1.02 (t, JHH 7.2 Hz, 12H, CH ), 2.71 (d, J 5.8 Hz, 2H,
2
Si, JSiC 8 Hz), 19.9 209.9 (d, JPC 11.4 Hz, vC
̲
P
91.0 (s, br,
1
(
d, JPC 20 Hz, C
JPC 4 Hz, CuC
p-C ), 133.2 (d, JPC 19 Hz, o-C
i-C
δSi −14.8. Anal. Found: C, 75.77; H, 8.59. Calcd for C H PSi: CuC
̲
H
2
P), 85.4 (d, JPC 5.4 Hz, C
̲
2
P), 104.7 (d, 74%). Propargyl tautomer (5%): NMR (C
6 6
D
3
̲
2
PC
6
5
3
PH
1
3
1
3
6
H
5
6
H
5
), 138.3 (d, JPC 16.5 Hz, CH
−13.6 (s, JSiP 19.7 Hz). Si{ H}-NMR:
2
P), 2.87 (m, 8H, NCH
), 19.8 (m, C P), 42.8 (d,
CH P), 87.6 (s, C
2 C
). C{ H}-NMR: δ 14.0 (d, JPC 5 Hz,
3
1
1
29
1
3
6
H
5
). P{ H}-NMR: δ
P
C
̲
3
̲
2
J
PC 17 Hz, NC
̲
2
), 81.5 (s,
uCCH P). P{ H}-NMR: δ 83.2 (s, br,
5%).
{(Et N)(Cl)P}C(Ph)vCvCH (16). To an ethereal solution of
2 2
3
1
1
̲
̲
24
33
2
2
P
C, 75.74; H, 8.74.
n
Bu
3
SiCuCCH
2
PPh
2
(13). As for 8, using HPPh
2
−3
(0.650 g,
.24 × 10− mol), BuLi (2.5 M, 1.15 cm , 2.87 × 10 mol) and 15 held at −78 °C was added drop-wise two equivalent of HCl
3
n
3
4
6
0
(0.784 g, 1.87 × 10− mol). Isolated as brown oil. Yield: (1 M in ether). The mixture was held at −78 °C while stirring
3
1
.95 g, 79%. NMR (C
6
D
6
, 30 °C): H-NMR: δ
H
0.6.3 (m, 6H, for 20 min, before being allowed to warm to ambient tempera-
3
SiCH ), 0.93 (t, J 7.2 Hz, 9H, CH ), 1.37 (m, 6H, CH CH Si), ture and stir overnight. The resulting suspension was filtered
2
HH
3
2
2
1
.41 (m, 6H, CH
3
CH
2
CH
2
), 2.76 (d, JPH 2.3 Hz, 2H, CH
2
P), and stripped of volatiles under reduced pressure, the resulting
1
7
.04–7.13 (m, 6H, m/p-P(C
6
H
5
)
2
), 7.41–7.46 (m, 4H, o-P(C
6
H
5
)
2
). orange oil was dried in vacuo. NMR (C
6
D
6
, 30 °C): H-NMR:
1
3
1
3
3
C{ H}-NMR: δC 13.7 (s, C
0 Hz, C P), 26.7 (s, CH
vCCH P), 104.0 (d, JPC 4.2 Hz, CuC
̲
̲
δH 0.81 (t, JHH 6.9 Hz, 6H, CH ), 2.94 (q, JHH 7.4 Hz, 4H,
3
2
3
PC
2
2
̲H
2
3
2
), 4.89 (dd, JHH 13.0 Hz, JPH 5.7 Hz, 1H, vCH
HH 13.0 Hz, JPH 5.7 Hz, 1H, vCH ), 6.94–7.02 (m, 1H,
p-C H ), 7.11 (7, J 7.8 Hz, 2H, m-C H ), 7.50 (d, J 7.8 Hz,
2
), 4.93 (dd,
2
(d, JPC 4.8 Hz, C
̲
2
P),
J
2
1
28.6 (d, JPC 6.4 Hz, m-C H ), 129.0 (s, p-C H ), 133.2 (d, J
6
5
6
5
PC
6
5
HH
6
5
HH
3
1
1
13
1
3
1
9 Hz, o-C
6
H
5
), 138.3 (d, JPC 15.5 Hz, i-C
6
H
5
). P{ H}-NMR: 2H, o-C
6
H
5
). C{ H}-NMR: δ
PC 13 Hz, NC ), 77.6 (s, vC
̲{ PCl(NEt )}vC), 135.4 (d, J 24 Hz, i-C H ), 127.6 (d,
C
13.9 (d, JPC 6.2 Hz, C
3
̲H ), 43.9
2
9
1
3
δ
P
−13.5 (s, JSiP 18.0 Hz). Si{ H}-NMR: δSi −12.9. Anal. Found: (d,
J
̲
2
̲H
2
), 105.3 (d, JPC 40 Hz,
C, 76.78; H, 9.32. Calcd for C H PSi: C, 76.73; H, 9.30.
PhC
2
7
39
2
PC
6
5
Me
2
PhSiCuCCH
2
P(SiMe
3
)
2
(14). In a manner similar to
J
PC 1.5 Hz, o-C
6
H
5
), 127.98 (s, p-C
6
H
5
) 128.9 (s, m-C
6 5
H ), 210.6
3
1
1
that described for 8, using HP(SiMe
3
)
2
(1.04 g, 5.84 × (d, JPC 8.4 Hz, vC
̲
P
122.0 (s, br, 77%).
−
3
n
3
−3
1
0
mol), BuLi (2.5 M, 2.3 cm , 5.75 × 10 mol) and 3
−
3
Platinum and palladium complexes
(1.25 g, 6.00 × 10 mol). Isolated as orange oil. Yield: 1.84 g,
1
9
2
0%. NMR (C
× Si(CH ) ), 0.44 (s, 2 × SiCH ), 2.43 (d, J 1.3 Hz, 2H, Pd) in DCM was added a cooled DCM solution of the respect-
PH
6 6 H 2 n
D , 30 °C): H-NMR: δ 0.25 (d, JPH 4.8 Hz, 18H, In a typical procedure, to a suspension of the [MCl ] (M = Pt,
3
3
3
This journal is © The Royal Society of Chemistry 2016
Dalton Trans., 2016, 45, 2148–2155 | 2153