S. Thoonen et al. / Tetrahedron 59 (2003) 10261–10268
10267
3
found to contain allyltin trichloride in 95% purity along with
some decomposition product (see text), corresponding to an
84% yield.
5.4 Hz, bipy 1), 8.25 (t, JHH¼6.9 Hz, bipy 2), 8.56 (t,
3JHH¼8.1 Hz, bipy 1), 8.70 (d, JHH¼8.1 Hz, bipy 2), 8.86
3
3
3
(d, JHH¼8.1 Hz, bipy 1), 9.04 (d, JHH¼8.1 Hz, bipy 2),
9.39 (d, 3JHH¼5.4 Hz, bipy 1), 9.57 (d, 3JHH¼5.4 Hz, bipy)
for the bipy resonances. An independently prepared sample
of (allyl)SnCl3 in acetone-d6 showed the same characteristic
4.1.2. Decomposition studies of allyltin trichloride.
Without solvent. A sample of freshly prepared (allyl)SnCl3
(3.4 g) was stored for several weeks in the dark at room
temperature. CH2Cl2 (10 mL) was added and the suspension
was filtrated. The white solid was washed two times with
CH2Cl2 (5 mL) and dried in vacuo (0.25 g). Elem. anal.
Found: Sn, 47.07; Cl, 31.43%. The volatiles from the filtrate
were removed in vacuo to give a brown sticky material
(3.0 g). Elem. anal. Found: C, 16.08; H, 2.38; Sn, 40.02; Cl,
36.03%. 1H NMR (CDCl3, 258C): d 0.6–2 (br, 3H), 2.2–2.6
(br, 9H), 5.3–5.6 (m, 2H), 5.7–5.9 (m, 1H). 13C NMR
(CDCl3, 258C): d 33.5, 39.8 (JCSn¼69.8 Hz),40 43.4, 123.5,
132.9 ppm.
1
resonances for CH2vCH–CH2C(CD3)2OSnCl3 in the H
NMR spectrum.4b
4.1.5. Reaction of (allyl)SnCl3 with acetone. Allyltin
trichloride (0.5 g, 1.8 mmol) was added dropwise to acetone
(5 mL) at room temperature. After ten minutes, H2O (2 mL)
was added to the reaction mixture followed by extraction
with Et2O (2x5 mL). The collected organic fractions
were dried with MgSO4 and filtered. Evaporation of the
solvent in vacuo yielded 0.15 g of a colourless oil. 1H NMR
(CDCl3, 258C): d 1.25 (s, 6H, CH3), 2.11 (s, 1H, OH), 2.25
3
(d, 2H, JHH¼8.0 Hz, CH2vCHCH2), 4.95–5.17 (m, 2H,
In CH2Cl2. Four aliquots of freshly prepared (allyl)SnCl3
(200 mg, 0.75 mmol) in 5 mL of CH2Cl2 with n-tridecane
(100 mL) were prepared. To the first and the second,
PtMe2(bipy) (38 mg, 0.1 mmol) and PdMe2(bipy) (29 mg,
0.1 mmol), respectively, were added. These two solutions
together with a solution that did not contain the metal
complex, were stored at 458C. The fourth solution was
stored at 258C. For the analysis of the reaction mixtures a
50 mL sample was taken and was reacted with 1.0 M
EtMgBr in Et2O (3 mL). The sample was quenched with
5 mL of water and the upper Et2O layer was analyzed by
GC.
CH2vCHCH2), 5.71–5.88 (1H, m, CH2vCHCH2). GC-
MS analysis 100 (1, Mþ), 85 (10, Mþ2CH3), 59 (100), 43
(55, Mþ2C3H5), 31 (22) (2-methyl-4-pentene-2-ol).
4.1.6. Reactions of MZ2(bipy) (M5Pd, Pt; Z5Me, Cl)
with 3-chloropropene or SnCl2. All experiments were
performed with 0.4 mmol of platinum- or palladium
complex and SnCl2 (302 mg, 1.6 mmol) or 3-chloropropene
(122 mg, 1.6 mmol) in 10 mL of CH2Cl2. The reaction
mixtures were analyzed by 1H NMR spectroscopy with
CDCl3 or acetone-d6 as solvent.
4.1.7. Stoichiometric reaction of PdMe2(bipy) with
3-chloropropene and SnCl2. To a mixture of 3-chloro-
propene (3 mL, 0.032 mmol), SnCl2 (6 mg, 0.032 mmol)
and CD2Cl2 (0.5 mL) in a NMR tube, PdMe2(bipy) (10 mg,
0.032 mmol) was added. The tube was stored at room
4.1.3. Synthesis of [Pd(h3-allyl)(bipy][SnCl3] (2).
PdCl(allyl)(bipy) (130 mg, 0.39 mmol) was suspended in
10 mL of CH2Cl2. SnCl2 (73 mg, 0.39 mmol) was added to
the suspension and the reaction mixture was stirred for 3
days at room temperature. Filtration of the reaction mixture
resulted in the isolation of a light yellow powder (133 mg,
65% yield). Mp 1828C (dec). 1H NMR (CD2Cl2, 2258C): d
1
temperature and the solution was analysed by H NMR
spectroscopy at regular intervals.
3
3.56 (d, 2H, JHH¼12.6 Hz, Pd–CH2), 4.28 (d, 2H,
4.1.8. Decomposition of [PtMe2(allyl)(SnCl3)(bipy)] (3).
A solution of 16 mg (0.024 mmol) of 3 in 1 mL of acetone-
d6 was transferred. After the tube was sealed, it was
submerged in a oil bath at 608C for 2 days. The NMR-tube
was cooled to room temperature and the solution was
analysed by 1H NMR spectroscopy at regular intervals.
After 48 h, an orange solid had precipitated from the
3
3JHH¼6.9 Hz, allylic CH2), 6.09 (m, 1H, JHH¼9.0 Hz),
7.71 (t, 2H, 3JHH¼7.2 Hz, bipy), 8.28 (t, 2H, 3JHH¼8.7 Hz,
3
bipy), 8.42 (d, 2H, JHH¼8.1 Hz, bipy), 8.83 (d, 2H,
3JHH¼4.8 Hz, bipy). 119Sn (CD2Cl2, 258C): d 237.0. Anal.
calcd. for C13H13Cl3N2PdSn: C, 29.53; H, 2.48; N, 5.30; Cl,
20.12. Found: C, 29.44; H, 2.40; N, 5.21; Cl, 20.16.
1
solution. H NMR (acetone-d6, 258C): d 2.19 (d, 2H, CH2,
3JHH¼5.0 Hz), 4.96–5.10 (m, 2H, CH2), 5.81–6.02 (m, 1H,
4.1.4. Reaction of [Pd(h3-allyl)(bipy][SnCl3] (2) with 3-
chloropropene or SnCl2. A solution of 2 (10 mg,
0.02 mmol) in 1 mL of CD2Cl2 or acetone-d6 was
4b
CH). An independently prepared sample of (allyl)SnCl3
showed the same resonances in the 1H NMR spectrum
recorded in acetone-d6.
transferred in
a
NMR tube. Next, SnCl2 (15 mg,
0.08 mmol) or 3-chloropropene (7 mL, 0.08 mmol) was
added. After the tube was sealed, it was stored at room
temperature or it was placed in an oil bath of 458C. The
1
solution was analysed by H NMR spectroscopy at regular
1
References
intervals. H NMR of the reaction with SnCl2 in CD2Cl2
3
(258C): d 3.40 (d, 2H, CH2, JHH¼13.2 Hz), 5.10 (d, 2H,
1. Ayrey, G.; Head, B. C.; Poller, R. C. Macromol. Rev. 1974, 8,
1–49.
3
CH2, JHH¼7.4 Hz), 5.23–5.44 (m, 1H, CH), 7.72 (t, 2H,
bipy, 3JHH¼13.2 Hz), 8.27 (t, 2H, bipy, 3JHH¼8.3 Hz), 8.35
2. Evans, C. J. In Chemistry of Tin; Harisson, P. G., Ed.; Blackie:
Glasgow, 1989; pp 421–453.
3
(d, 2H, bipy, JHH¼7.4 Hz), 8.82 (d, 2H, bipy,
3JHH¼6.4 Hz). 1H NMR of the reaction with SnCl2 in
3 (a) Bokranz, A.; Plum, H. Fortschr. Chem. Forsch. 1971, 16,
365–403. (b) Moedritzer, K. Organomet. Chem. Rev. 1966,
179–278. (c) Ingham, R. K.; Rosenberg, S. D.; Gilman, H.
Chem. Rev. 1960, 60, 459–539.
3
acetone-d6 (258C): d 2.19 (d, 2H, CH2, JHH¼5.0 Hz),
4.96–5.10 (m, 2H, CH2), 5.81–6.02 (m, 1H, CH) for
CH2vCH–CH2C(CD3)2OSnCl3 and d 8.09 (t, JHH
3
¼