MOLYBDENUM TIN-CONTAINING π-COMPLEXES
21
2
124.9 (Cm) 79.8 q (OCMe2CF3, JCF 28.9), 58.9
(CH2=CHSnMe3), 56.7 (CH2=CHSnMe3), 29.2 and
28.8 (CHMe2), 28.5 (CHMe2), 23.98 and 22.9
(2,6-diisopropylphenylimido)bis(1,1-di-methyl-2,2,2-
triftoretanolato)(trimethylvinylstannane)molybdenum
II and 2-methyl-2-phenyl-5-(triethyl-stannyl)pent-3-
ene. The overall yield of compounds was 0.17 g
(94%). The resulting π-complex (Et3SnCH=CH2)Mo·
(N-2,6-Pri2C6H3)(OCMe2CF3)2 was a mixture of two
1
(OCMe2CF3), –7.89 (SnCH3). Isomer 2 (38%), H
NMR spectrum (C6D6, δ, ppm, J, Hz): 6.97 br.s (3H,
3
H
arom), 3.82 sept (2H, CHMe2, JHH 6.8), 3.62 d (1H,
CH2=CHSnMe3, 3JHH 12.05), 2.43
d
(1H,
isomers with a ratio of 74:26%. Isomer 1 (74%). H
1
CH2=CHSnMe3, 3JHH 12.05), 1.36 and 1.32 s (6H each,
NMR spectrum (δ, ppm, J, Hz): 6.97 br.s (3H, Harom),
2
3
OCMe2CF3), 1.26 d (12H, CHMe2, JHH 6.8), 0.07 s
3.85 sept (2H, CHMe2, JHH 6.8), 2.70 m (2H,
[9H, Sn(CH3)3]. 13C NMR spectrum (C6D6, δ, ppm, J,
CH2=CHSnEt3 JHH 14.5), 2.05 t (1H, CH2=CHSnEt3,
3
Hz): 149.6 (Cipso), 145.5 (Co), 128.0 (Cp) 126.2 q
3JHH 14.5), 1.38 and 1.35 s (6H each, OCMe2CF3),
1
2
(OCMe2CF3 JCF 276.0), 124.9 (Cm), 79.8 q (OCMe2F3,
1.24 d (12H, CHMe2, JHH 6.5), 1.17 t (9H,
2JCF 28.9), 73.8 (CH2=CHSnMe3), 68.9
(CH2=CHSnMe3), 29.2 and 28.8 ( CHMe2), 28.5
(CHMe2), 23.98 and 22.9 (OCMe2CF3), –7.89 (SnCH3).
SnCH2CH3, JHH 7.9), 0.85 q (6H, SnCH2CH3, JHH
7.8). 13C NMR spectrum (C6D6, δ, ppm, J, Hz): 150.0
(Cipso), 145.8 (Co), 128.0 (Cp) 127.5 q (OCMe2CF3,
1JCF 286.0), 123.3 (Cm), 79.3 q (OCMe2CF3, 2JCF 28.5),
58.0 (CH2=CHSnEt3), 57.9 (CH2=CHSnEt3), 29.9 and
29.5 (CHMe2) , 28.6 (CHMe2), 24.1 and 23.3 (OCMe2
CF3), 2.4 (SnCH2CH3), 1.02 (SnCH2CH3). 119Sn NMR
2
2
2-Methyl-2-phenyl-5-(trimethylstannyl)pent-3-ene.
After fractionation of the reaction mixture in vacuum
(10–2 mm Hg) at 100–110°C the olefin derivative
PhMe2CCH=CHCH2SnMe3 was isolated as air stable
colorless oil. Yield 0.05 g (62%). IR spectrum, ν, cm–1:
3083 w, 3060 w (Carom–H), 2966 s, 2914 s, 2869 m
1
spectrum (C6D6, δ, ppm): 36.2. Isomer 2 (26%), H
NMR spectrum (C6D6, δ, ppm, J, Hz): 6.97 br.s (3H,
3
H
arom), 3.85 sept (2H, CHMe2 JHH 6.8), 3.26 d.d (1H,
(C–H, CH3), 1646 w (C=C), 1600 w, 1492 m (Carom
arom, Ph), 1462 m (C–H, CH3), 1446 m (CH, CH2Sn),
–
2
3
CH2=CHSnEt3 JHH 2.2, JHH 14.0), 3.11 t (1H,
C
CH2=CHSnEt3, 3JHH 14.0), 2.39 d.d (1H,
1383 w (C–H, CH3), 1186 w (C–H, CH3), 1100 m,
1030 m (CH, SnMe3), 698 m, 763 m (Carom–H), 527 m,
512 [Sn–C, Sn(CH3)3]. Signals in the 1H and 13C NMR
spectra of the isolated compounds correspond to the
signals of PhMe2CCH=CHCH2SnMe3 in the reaction
2
3
CH2=CHSnEt2 JHH 2.5, JHH 14.0), 1.38 and 1.35 s
2
(6H each, OCMe2CF3), 1.24 d (12H, CHMe2, JHH
2
6.5), 1.17 t (9H, SnCH2CH3, JHH 7.9), 0.85 q (6H,
SnCH2CH3, JHH 7.8). 13C NMR spectrum (C6D6, δ,
2
ppm, J, Hz): 150.0 (Cipso), 145.8 (Co), 128.0 (Cp),
1
mixture prior to frac-tionation. H NMR spectrum
1
127.5 q (OCMe2CF3, JCF 286.0), 123.3 (Cm), 79.3 q
2
(C6D6, δ, ppm, J, Hz): 7.35 d (2H, Harom, JHH 7.8),
2
(OCMe2CF3, JCF 28.5), 70.6 (CH2=CHSnEt3), 66.0
7.30 t (2H, Harom, 2JHH 7.4), 7.18 t (1H, Harom, 2JHH 7.2),
5.48 m (2H, CH=CH, 2JHH 7.8, 3JHH 15.4), 1.76 d (2H,
CH2Sn, JHSn 64.4), 1.38 s (6H, CMe2Ph), 0.09 s (9H,
SnCH3, JHSn 51.9). 13C NMR spectrum (C6D6, δ, ppm):
149.91 (Cipso, Ph), 136.03 (CH=CH), 127.92 (Cm, Ph),
126.23 (Co, Ph), 125.48 (Cp, Ph), 125.06 (CH=CH),
40.35 (CMe2Ph), 29.34 (CMe2Ph), 16.11 (CH2Sn),
–10.13 (SnCH3). 119Sn NMR spectrum (C6D6, δ, ppm):
–2.9. Found, %: C 56.19, H 7.71. C15H24Sn.
Calculated, %: C 55.8, H 7.44.
(CH2=CHSnEt3), 29.9 and 29.5 (CHMe2), 28.6
(CHMe2), 24.11 and 23.3 (OCMe2CF3), 2.41
(SnCH2CH3), 1.02 (SnCH2CH3). 119Sn NMR spectrum
(C6D6, δ, ppm): 91.1.
2-Methyl-2-phenyl-5-(triethylstannyl)pent-3-ene.
The olefin derivative PhMe2CCH=CHCH2SnEt3 was
isolated by fractionation of the reaction mixture in a
vacuum (10–2 mm Hg) at 100–110°C as air stable,
colorless oil. Yield 0.04 g (80%). IR spectrum (ν, cm–1:
3083 w, 3060 w, 3022 w (Carom–H), 2955 m, 2943 s,
2900 s, 2865 (C–H, CH3, CH2), 1645 w (C=C), 1600
w, 1490 w (Carom–Carom, Ph), 1460 m, 1420 m (C–H,
CH3, CH2), 1380 w, 1360 w (C–H, CH3), 1258 w
(C–H, CH3, C(CH3)2Ph), 1232 w, 1186 w (C–H, CH3),
1096 m, 1017 m. (Carom–H, Ph), 969 m, 807 m
(HC=CH), 761 m (Carom–H), 742 (C–H, CH2–Sn) 506
(2,6-Diisopropylphenylimido)bis(1,1-dimethyl-2,2,2-
trifluoroethanolato)(triethylvinylstannane)molyb-
denum (II). To a solution of PhMe2CC(H)=Mo(N-2,6-
Pri2C6H3)(OCMe2CF3)2 0.11 g (0.16 mmol) in 1.5 ml of
deuterobenzene 0.07 g (0.3 mmol) of Et3SnCH=CH2
1
was added at room temperature. According to the H
NMR spectroscopy, the reaction was completed at
room temperature within 5 min. The solvent was
removed by evaporation in vacuum at room tem-
perature. The red-brown oily residue was a mixture of
m (Sn–C, SnEt3). 1H NMR spectrum (C6D6, δ, ppm, J,
2
Hz): 7.38 d (2H, Harom, JHH 7.5), 7.24 t (2H, Harom
,
2JHH 7.2), 7.14 t (1H, Harom, JHH 6.9), 5.57 m (2H,
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012