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A. J. Nawara-Hultzsch et al. · Palladium, Platinum, and Borane Adducts of Symmetrical Trialkylphosphines
1
1
trans-3c as a yellow oil (0.322 g, 0.355 mmol, 88 %). – t [36], JCP = 13.5 Hz, PCH2); 31P{ H}: δ = 8.3 (s). – IR
Anal. for C48H90Cl2P2Pd: calcd. C 63.62, H 9.94; found (cm−1, oil film): ν = 3076 (w), 2926 (s), 2856 (m), 1640
1
C 63.44, H 9.93. – NMR (CDCl3) [35]: H: δ = 5.82 (ddt, (m), 1459 (m), 1417 (m), 992 (m), 907 (s), 791 (m), 718
6H, 3JHHtrans = 17.1 Hz, 3JHHcis = 10.3 Hz, 3JHH = 6.6 Hz, (m). – MS [34]: m/z (%) = 747 (100) [M–Br]+, 665 (50)
CH=), 4.95 (br d, 6H, 3JHHtrans = 17.2 Hz, =CHEHZ), 4.88 [M–2Br]+, 560 (50) [P((CH2)4CH=CH2)3]+.
(br d, 6H, 3JHHcis = 9.1 Hz, =CHEHZ), 2.09 – 2.03 (m, 12H,
PdBr (P((CH ) CH=CH ) ) (4b)
CH2CH=), 1.79 – 1.75 (m, 12H, PCH2), 1.61 – 1.50 (m, 12H,
2
2 5
2 3 2
1
PCH2CH2), 1.45 – 1.29 (m, 36H, remaining CH2); 13C{ H}:
Phosphine 1b (0.479 g, 1.49 mmol), PdBr2(COD)
(0.278 g, 0.743 mmol) [19], and CH2Cl2 (15 mL) were
combined in a procedure analogous to that for 4a [37]. An
identical workup gave trans-4b as an orange oil (0.413 g,
0.453 mmol, 61 %). – Anal. for C42H78Br2P2Pd: calcd.
C 55.36, H 8.63; found C 56.13, H 8.94 [38]. – NMR
δ = 139.2 (s, CH=), 114.5 (s, =CH2), 34.0 (s, CH2CH=),
3
31.3 (virtual t [36], JCP = 6.4 Hz, PCH2CH2CH2), 29.0
(s, CH2), 28.9 (s, CH2), 24.2 (s, PCH2CH2), 21.7 (virtual
1
1
t [36], JCP = 13.0 Hz, PCH2); 31P{ H}: δ = 11.5 (s). –
IR (cm−1, oil film): ν = 3076 (w), 2926 (s), 2856 (m),
1640 (m), 1459 (m), 1440 (m), 1417 (m), 992 (m), 907 (s),
799 (w), 733 (s), 566 (s). – MS [34]: m/z (%) = 365 (100)
[P((CH2)6CH=CH2)3]+.
(CDCl3) [35]: 1H: δ = 5.76 (ddt, 6H, JHHtrans = 17.1 Hz,
3
3JHHcis = 10.1 Hz, JHH = 6.6 Hz, CH=), 4.94 (br d, 6H,
3
3JHHtrans = 17.1 Hz, =CHEHZ), 4.84 (br d, 6H, JHHcis
=
3
10.2 Hz, =CHEHZ), 2.09 – 2.03 (br m, 12H, CH2CH=),
2.03 – 1.95 (br m, 12H, PCH2), 1.79 – 1.43 (br m, 36H, re-
PdCl (P((CH ) CH=CH ) ) (3e)
2
2 8
2 3 2
1
maining CH2); 13C{ H}: δ = 138.7 (s, CH=), 115.1 (s,
Phosphine 1e (1.701 g, 3.79 mmol), PdCl2(COD)
(0.541 g, 1.89 mmol) [19], and CH2Cl2 (20 mL) were com-
bined in a procedure analogous to that for 3a [32]. A simi-
lar workup (2.5 × 16 cm column) gave trans-3e as a yellow
3
= CH2), 33.6 (s, CH2CH=), 30.6 (virtual t [36], JCP
=
6.5 Hz, PCH2CH2CH2), 24.1 (s, PCH2CH2CH2CH2), 23.5
1
(s, PCH2CH2), 23.3 (virtual t [36], JCP = 13.5 Hz, PCH2);
1
31P{ H}: δ = 8.3 (s). – IR (cm−1, oil film): ν = 2926 (s),
1
oil (1.530 g, 1.42 mmol, 75 %). – NMR (CDCl3) [35]: H:
3
3
2856 (m), 1640 (m), 1459 (m), 1417 (m), 992 (m), 907 (s),
791 (m), 718 (m). – MS [34]: m/z (%) = 831 (100) [M–Br]+,
750 (80) [M–2Br]+, 664 (50) [P((CH2)5CH=CH2)3]+.
δ = 5.82 (ddt, 6H, JHHtrans = 16.9 Hz, JHHcis = 10.1 Hz,
3JHH = 6.6 Hz, CH=), 4.98 (br d, 6H, JHHtrans = 17.1 Hz,
3
3
=CHEHZ), 4.94 (br d, 6H, JHHcis = 10.1 Hz, =CHEHZ),
2.15 – 1.98 (m, 12H, CH2CH=), 1.98 – 1.88 (br m, 12H,
PCH2), 1.70 – 1.68 (br m, 12H, PCH2CH2), 1.50 – 1.18 (br
PdBr (P((CH ) CH=CH ) ) (4c)
2
2 6
2 3 2
1
m, 60H, remaining CH2); 13C{ H}: δ = 139.1 (s, CH=),
Phosphine 1c (1.163 g, 3.19 mmol), PdBr2(COD)
(0.675 g, 1.80 mmol) [19], and CH2Cl2 (20 mL) were com-
bined in a procedure analogous to that for 4a [37]. A similar
workup (1.5 × 12 cm column) gave trans-4c as an orange
oil (0.879 g, 0.883 mmol, 55 % based upon limiting 1c). –
Anal. for C48H90Br2P2Pd: calcd. C 57.92, H 9.11; found
114.0 (s, =CH2), 33.8 (s, CH2CH=), 31.2 (virtual t [36],
3JCP = 6.4 Hz, PCH2CH2CH2), 29.6 (s, CH2), 29.4 (s, CH2),
29.1 (s, CH2), 28.9 (s, CH2), 24.0 (s, PCH2CH2), 21.4 (vir-
1
tual t [36], 1JCP = 16.1 Hz, PCH2); 31P{ H}: δ = 11.4 (s). –
IR (cm−1, oil film): ν = 3078 (m), 2923 (s), 2854 (s), 1642
(m), 1465 (m), 1441 (s), 992 (m), 907 (s), 722 (m). – MS
[34]: m/z (%) = 449 (100) [P((CH2)8CH=CH2)3]+.
1
C 58.15, H 9.31. – NMR (CDCl3 [35]): H: δ = 5.77 (ddt,
6H, 3JHHtrans = 16.9 Hz, 3JHHcis = 10.1 Hz, 3JHH = 6.6 Hz,
CH=), 4.95 (br d, 6H, 3JHHtrans = 17.0 Hz, =CHEHZ), 4.89
(br d, 6H, 3JHHcis = 10.2 Hz, =CHEHZ), 2.03 – 1.99 (m, 12H,
CH2CH=), 1.92 – 1.90 (m, 12H, PCH2), 1.50 – 1.48 (m, 12H,
PdBr (P((CH ) CH=CH ) ) (4a)
2
2 4
2 3 2
Phosphine 1a (0.400 g, 1.43 mmol), PdBr2(COD)
(0.233 g, 0.622 mmol) [19], and CH2Cl2 (10 mL) were com-
bined in a procedure analogous to that for 3a [37]. A similar
workup (1.5 × 7 cm column) gave trans-4a as an orange oil
(0.316 g, 0.382 mmol, 61 %). – Anal. for C36H66Br2P2Pd:
calcd. C 52.28, H 8.04; found C 53.04, H 8.23 [38]. – NMR
PCH2CH2), 1.42 – 1.29 (m, 36H, remaining CH2); 13C{ H}:
1
δ = 139.2 (s, CH=), 114.3 (s, = CH2), 33.8 (s, CH2CH=),
3
31.0 (virtual t [36], JCP = 6.5 Hz, PCH2CH2CH2), 28.8
(s, CH2), 28.7 (s, CH2), 24.2 (s, PCH2CH2), 23.3 (virtual
1
1
t [30], JCP = 13.5 Hz, PCH2); 31P{ H}: δ = 8.2 (s). – IR
(cm−1, oil film): ν = 3076 (w), 2926 (s), 2856 (m), 1640
(m), 1459 (m), 1440 (m), 1413 (m), 992 (m), 907 (s), 795
(m), 718 (m). – MS [34]: m/z (%) = 916 (5) [M–Br]+, 365
(100) [P((CH2)6CH=CH2)3]+.
1
3
(CDCl3) [35]: H: δ = 5.76 (ddt, 6H, JHHtrans = 17.0 Hz,
3JHHcis = 10.2 Hz, JHH = 6.6 Hz, CH=), 4.98 (br d, 6H,
3
3JHHtrans = 17.1 Hz, =CHEHZ), 4.93 (br d, 6H, JHHcis
=
3
10.1 Hz, =CHEHZ), 2.09 – 2.03 (br m, 12H, CH2CH=),
2.03 – 1.95 (br m, 12H, PCH2), 1.80 – 1.41 (br m, 24H, re-
PtCl (P((CH ) CH=CH ) ) (5b)
2
2 5
2 3 2
1
maining CH2); 13C{ H}: δ = 138.7 (s, CH=), 115.1 (s,
3
= CH2), 33.6 (s, CH2CH=), 30.6 (virtual t [36], JCP
=
A. A Schlenk flask was charged with 1b (0.299 g,
6.5 Hz, PCH2CH2CH2), 24.1 (s, PCH2CH2), 23.3 (virtual 0.936 mmol), PtCl2 (0.123 g, 0.469 mmol), and C6H6
- 10.1515/znb-2010-0327
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