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Can. J. Chem. Vol. 84, 2006
4H, J = 7.4 Hz, Ar), 7.17 (t, 4H, J = 7.5 Hz, Ar), 7.12 (d,
4H, J = 7.2 Hz, Ar), 4.91 (t, 2H, J = 8.4 Hz, CH2), 2.03 (s,
31P{1H} NMR (CDCl3) δ: –80.3 (s, JPtP = 3056 Hz). Mass
spectrum (FAB) m/z: 715 [M+ – Br], 634 [M+ – 2Br]. Anal.
calcd. for PtBr2P2C29H30·CH2Cl2: C 40.90, H 3.52, Br 18.18,
P 7.04; found: C 40.92, H 4.44, Br 16.74, P 7.30.
12H, Me). 31P{1H} NMR (CDCl3) δ: –37.7 (s, JWP
=
197 Hz). Mass spectrum (FAB) m/z: 736 [M+], 707 [M+ –
CO], 680 [M+ – 2CO], 622 [M+ – 4CO]. Anal. calcd. for
WP2O4C33H30·0.5CH2Cl2: C 51.64, H 3.98, P 7.96; found: C
52.45, H 3.98, P 7.69.
Preparation of cis-[PtI2(2-dotpm)] (5c)
5a (0.05 g, 0.08 mmol) and LiI (0.02 g, 0.15 mmol) were
dissolved in THF (15 cm3) and the yellow solution was
stirred at room temperature for 20 h. Removal of volatiles
under reduced pressure yielded a yellow solid. This was
redissolved in dichloromethane and was washed three times
with water. The yellow solution was pumped to dryness un-
der reduced pressure to give 5c as a yellow powder (0.04 g,
Preparation of [CpRuCl(2-dotpm)] (4)
[CpRuCl(PPh3)2] (0.37 g, 0.51 mmol) and dotpm
(0.224 g, 0.51 mmol) were refluxed in toluene (100 cm3) for
24 h. Chromatography on silica eluting with diethyl ether –
light petroleum (2:1) gave a yellow band of [CpRuCl(PPh3)2],
which was discarded. Eluting with diethyl ether – light pe-
troleum (1:1) gave an orange band, which yielded 4 as an or-
ange solid (0.14 g, 76%). IR (KBr, cm–1): 1448 (m), 1132
(m), 1091 (m), 1089 (m), 1066 (m), 804 (m), 748 (s), 725
1
62%). H NMR (CDCl3) δ: 7.97 (q, 4H, J = 7.7 Hz, Ar),
7.43 (t, 4H, J = 7.6 Hz, Ar), 7.23 (t, 8H, J = 7.7 Hz, Ar),
4.78 (t, 2H, J = 10.3 Hz, CH2), 2.28 (s, 12H, Me). 31P{1H}
NMR (CDCl3) δ: –87.7 (s, JPtP = 2876 Hz). Mass spectrum
(FAB) m/z: 889 [M+], 762 [M+ – I]. Anal. calcd. for
PtP2I2C29H30: C 39.15, H 3.37, I 28.57, P 6.97; found: C
39.08, H 3.69, I 28.63, P 7.18.
1
(s), 709 (m), 461 (s). H NMR (CD2Cl2, 308 K) δ: 8.08 (br,
2H, Ar), 7.42–7.15 (m, 8H, Ar), 7.08 (d, 2H, J = 7.4 Hz,
Ar), 7.04 (br d, 2H, Ar), 6.73 (t, 2H, J = 7.4 Hz, Ar), 4.94
(dt, 1H, J = 13.8, 8.1 Hz, CH2), 4.75 (s, 5H, Cp), 4.54 (q,
1H, J = 10.9 Hz, CH2), 2.08 (s, 6H, Me), 2.05 (s, 6H, Me);
(228 K) δ: 8.51 (br, 1H, Ar), 7.58 (br, 1H, Ar), 7.40–6.95
(m, 11H, Ar), 6.86 (t, 1H, J = 7.1 Hz, Ar), 6.43 (br, 1H, Ar),
6.36 (br, 1H, Ar), 4.76 (br, 1H, CH2), 4.75 (s, 5H, Cp), 4.46
(br, 1H, CH2), 2.24 (s, 3H, Me), 2.13 (s, 3H, Me), 1.86 (s,
6H, CH3). 31P{1H} NMR (CDCl3) δ: –4.7 (s). Mass spec-
trum (FAB) m/z: 642 [M+], 607 [M+ – Cl], 576 [M+ – Cp].
Anal. calcd. for C34H35P2ClRu·CHCl3·2H2O: C 51.53, H
5.15; found: C 51.63, H 4.34.
Preparation of cis-[PdCl2(2-dotpm)] (6)
cis-[Pd(PhCN)2Cl2] (0.16 g, 0.42 mmol) and dotpm
(0.19 g, 0.42 mmol) were dissolved in dry dichloromethane
(15 cm3) and this was refluxed for 20 h. Removal of
volatiles under reduced pressure gave 6 as a brown powder
(0.19 g, 75%), which was washed with methanol and was
air-dried. IR ν(CH) (KBr, cm–1): 3055 (w), 2963 (w), 2920
1
(w). H NMR (CDCl3) δ: 7.97 (dd, 4H, J = 8.2 Hz, 7.7, Ar),
7.45 (t, 4H, J = 7.6 Hz, Ar), 7.23–7.19 (m, 8H, Ar), 4.33 (t,
2H, J = 9.9 Hz, CH2), 2.32 (s, 12H, Me). 31P{1H} NMR
(CDCl3) δ: –69.0 (s). Mass spectrum (FAB) m/z: 583 [M+ –
Cl], 545 [M+ – 2Cl]. Anal. calcd. for PdP2Cl2C29H30·0.2
PhCN: C 54.83, H 4.85, N 0.44, Cl 11.11, P 9.70; found: C
54.49, H 4.54, N 0.44, Cl 12.80, P 9.70.
2
Preparation of cis-[PtCl2(η -dotpm)] (5a)
cis-[Pt(PhCN)2Cl2] (0.21 g, 0.44 mmol) and dotpm
(0.21 g, 0.44 mmol) were dissolved in dry dichloromethane
(15 cm3) and the solution was refluxed for 10 h. A white
precipitate was formed and after cooling, hexane (ca. 15 cm3)
was added to precipitate more solids. The mixture was fil-
tered and the residue was washed with hexane and air-dried.
A white powder was obtained, which was recrystallized
from dichloromethane and methanol to yield 5a as colorless
plates (0.28 g, 92%). IR ν(CH) (KBr, cm–1): 3056 (w), 3011
2
Preparation of cis-[Cr(CO)4(η -Medotpm)] (7)
1 (0.33 g, 0.55 mmol) was dissolved in dry THF (25 cm3).
n-BuLi (0.7 cm3, 1.09 mmol) was added and the yellow so-
lution immediately darkened. After stirring at room tempera-
ture for 1 h, MeI (0.07 cm3, 1.09 mmol) was added and the
color lightened. The reaction mixture was stirred for 20 h
and pumped to dryness under reduced pressure. The solid
was redissolved in dichloromethane and was washed thor-
oughly with distilled water. The dichloromethane extract
was dried over MgSO4 and filtered. Removal of volatiles un-
der reduced pressure yielded a yellow powder that was
recrystallized from dichloromethane and methanol to give 7
as yellow crystals (0.33 g, 99%). IR ν(CO) (CH2Cl2, cm–1):
1
(w), 2960 (w), 2919 (w), 2904 (w), 2856 (w). H NMR
(CDCl3) δ: 7.96 (dd, 4H, J = 8.1, 7.9 Hz, Ar), 7.43 (t, 4H,
J = 7.3 Hz, Ar), 7.23–7.20 (m, 8H, Ar), 4.59 (t, 2H, J =
10.0 Hz, CH2), 2.26 (s, 12H, Me). 31P{1H} NMR (CDCl3) δ:
–77.9 (s, JPtP = 3097 Hz). Mass spectrum (FAB) m/z: 1484
[2M++ 2Cl], 1409 [2M+], 742 [M+ + Cl], 671 [M+ – Cl], 634
[M+ – 2Cl]. Anal. calcd. for PtP2Cl2C29H30: C 49.29, H 4.25,
Cl 10.06, P 8.78; found: C 48.70, H 4.08, Cl 10.75, P 8.48.
1
2006 (s), 1913 (s), 1893 (s), 1865 (s). H NMR (CDCl3) δ:
Preparation of cis-[PtBr2(2-dotpm)] (5b)
8.27–8.26 (m, 4H, Ar), 7.38–7.33 (m, 8H, Ar), 7.05 (m, 4H,
Ar), 5.39 (sextet, 1H, J = 7.2 Hz, CH), 2.09 (s, 6H, Me),
2.00 (s, 6H, Me), 1.06 (dt, 3H, J = 15.9, 7.3 Hz, Me).
31P{1H} NMR (CDCl3) δ: 27.8 (s). Mass spectrum (FAB) m/z:
618 [M+], 562 [M+ – 2CO], 534 [M+ – 3CO], 506 [M+ –
4CO]. Anal. calcd. for CrP2O4C34H32·0.75CH2Cl2: C 61.17,
H 4.91, P 9.09; found: C 60.64, H 4.96, P 9.21.
5a (0.05 g, 0.08 mmol) and LiBr (0.01 g, 0.15 mmol)
were dissolved in dry THF (15 cm3) and the mixture was
stirred at room temperature for 20 h. The solvent was dis-
tilled off and the residue was redissolved in dichloro-
methane. This was washed thoroughly with distilled water
and the dichloromethane extract was dried over MgSO4. Re-
moval of volatiles under reduced pressure gave 5b as a yel-
low powder (0.05 g, 78%). 1H NMR (CDCl3) ␦: 7.98 (q, 4H,
J = 7.7 Hz, Ar), 7.44 (t, 4H, J = 7.3 Hz, Ar), 7.23–7.21 (m,
8H, Ar), 4.65 (t, 2H, J = 10.2 Hz, CH2), 2.27 (s, 12H, Me).
Preparation of cis-[Mo(CO)4(2-Medotpm)] (8)
2 (0.30 g, 0.46 mmol) was dissolved in dry THF (15 cm3).
n-BuLi (0.37 cm3, 0.60 mmol) was added to the yellow solu-
© 2006 NRC Canada