312
P. Bagi et al. / Journal of Organometallic Chemistry 751 (2014) 306e313
was filtered and the mother liquor was concentrated to give
0.13 g (85%) of 6a as a 1:1 mixture of the homo- ((R,R) and (S,S))
and the heterochiral (R,S) forms.
C3eCH3), 1.89e2.05 (m, 2H, PCH2), 2.08e2.15 (m, 1H, CHMe2),
2.66e3.11 (m, 4H, CH2PCH2), 5.50 (d, J ¼ 24.1, 1H, CH]); HRMS
[M ꢀ Cl]þ
¼ 541.1465, C18H34P2ClPt requires 541.1451 for the
31P NMR (CDCl3)
d
21.19 (JPteP
¼
3450, 50%), 21.21
35Cl and 19fo5uPntdisotopes.
(JPteP ¼ 3451, 50%); 13C NMR (CDCl3)
d
8.9 (3JPteC ¼ 25, CH2CH3),
The optically active cis-[bis(1-isobutyl-3-methyl-3-phos-
pholeno)-dichloro-platinum(II)] ((R,R)-6b) was prepared analo-
gously from (R)-1-isobutyl-3-methyl-3-phospholene-1-oxide ((R)-
3b) and was obtained with an ee of 96%. Yield of (R,R)-6b: 91%;
18.8e19.1 (m, C3eCH3), 21.3 (2JPteC ¼ 37, JPeC ¼ 43, JPeC ¼ 7,
1
3
PCH2), 31.8e32.6 (m, C5), 35.5e36.3 (m, C2), 122.1e122.5 (m, C4),
138.6e139.0 (m, C3); 1H NMR (CDCl3)
d 1.15e1.22 (m, 3H,
CH2CH3), 1.83 (bs, 3H, C3eCH3), 2.02e2.09 (m, 2H, PCH2), 2.67e
3.05 (m, 4H, CH2PCH2), 5.50 (d, J ¼ 23.0, 1H, CH]); HRMS
½
a 2D5
ꢃ
¼ ꢀ8.6 [c 0.9, CHCl3]; 31P NMR (CDCl3)
d
16.2 (JPteP ¼ 3449);
3
5
13C NMR (CDCl3)
d
19.0 (4JPteC ¼ 40, JPeC ¼ 4, JPeC ¼ 4, C3eCH3),
[M ꢀ Cl]þ
¼ 485.0810, C14H26P2ClPt requires 485.0825 for
24.8 (4JPteC ¼ 34, 3JPeC ¼ 4, 5JPeC ¼ 4) and 24.9 (4JPteC ¼ 34, 3JPeC ¼ 4,
found
the 35Cl and 195Pt isotopes.
5JPeC ¼ 4) CH(CH3)2, 25.7 (3J
¼ 16, CHMe2), 33.5 (2JPteC ¼ 57,
PteC
The optically active cis-[bis(1-ethyl-3-methyl-3-phospholeno)-
dichloro-platinum(II)] ((S,S)-6a) was prepared similarly from (S)-1-
ethyl-3-methyl-3-phospholene-1-oxide ((S)-3a) with an ee of 83%.
1JPeC ¼ 44, 3JPeC ¼ 5, PCH2), 36.9 (2JPteC ¼ 48, 1JPeC ¼ 41, 3JPeC ¼ 7,
C5), 37.3 (2JPteC ¼ 42, 1JPeC ¼ 48, 3JPeC ¼ 5, C2), 122.0 (3JPteC ¼ 31, C4),
138.9 (3JPteC ¼ 31, 2JPeC ¼ 2, 4JPeC ¼ 2, C3); 1H NMR (CDCl3)
d 1.13 (d,
Yield of (S,S)-6a: 55%; ½a D25
ꢃ
¼ ꢀ1.3 [c 1.2, CHCl3]; 31P NMR (CDCl3)
J ¼ 6.5, 3H) and 1.17 (d, J ¼ 6.5, 3H) CH(CH3)2, 1.84 (bs, 3H, C3eCH3),
d
21.2 (JPteP ¼ 3451); 13C NMR (CDCl3)
d
8.9 (3JPteC ¼ 25, CH2CH3),
1.89e2.05 (m, 2H, PCH2), 2.08e2.17 (m, 1H, CHMe2), 2.72e3.11 (m,
3
5
18.9 (4JPteC ¼ 30, JPeC ¼ 5, JPeC ¼ 5, C3eCH3), 21.3 (2JPteC ¼ 37,
1JPeC ¼ 42, 3JPeC ¼ 7, PCH2), 32.2 (2JPteC ¼ 53, 1JPeC ¼ 47, 3JPeC ¼ 6,
C5), 35.7 (2JPteC ¼ 41, 1JPeC ¼ 48, 3JPeC ¼ 6, C2), 122.2 (3JPteC ¼ 30, C4),
4H, CH2PCH2), 5.50 (d,
¼ 541.1454, C18H34P2ClPt requires 541.1451 for the
35Cl and 19fo5uPntdisotopes.
J
¼
22.6, 1H, CH]); HRMS
[M ꢀ Cl]þ
138.7 (3JPteC ¼ 31, 3JPeC ¼ 2, 5JPeC ¼ 2, C3); 1H NMR (CDCl3)
d 1.16e
1.23 (m, 3H, CH2CH3), 1.82 (bs, 3H, C3eCH3), 2.01e2.11 (m, 2H,
PCH2), 2.53e2.75 (m, 4H, CH2PCH2), 5.52 (d, J ¼ 23.5, 1H, CH¼);
4.11. Preparation of 1-isopentyl-3-methyl-3-phospholene-borane
(5c)
HRMS [M ꢀ Cl]þ
¼ 485.0828, C14H26P2ClPt requires 485.0825
found
for the 35Cl and 195Pt isotopes.
Racemic 1-isopentyl-3-methyl-3-phospholene 1-oxide (3c)
(0.41 g (2.2 mmol)) was transformed to phospholene-borane 5c
analogously to the 3a / 4a / 5a conversion. Yield: 44%; 31P NMR
4.9. Preparation of 1-isobutyl-3-methyl-3-phospholene-borane
(5b)
(CDCl3)
d
33.3 (broad); 13C NMR (CDCl3)
d
19.1 (3JPeC ¼ 7.5, C3eCH3),
22.1 (CH(CH3)2), 23.3 (1JPeC ¼ 30.7, PCH2), 29.2 (3JPeC ¼ 12.2,
CHMe2), 29.9 (1JPeC ¼ 34.1, C5), 31.7 (2JPeC ¼ 2.1, CH2CH2CH), 33.8
(1JPeC ¼ 35.8, C2), 121.9 (C4), 137.9 (2JPeC ¼ 2.5, C3); 1H NMR (CDCl3)
Racemic 1-isobutyl-3-methyl-3-phospholene 1-oxide (3b)
(0.38 g (2.2 mmol)) was transformed to phospholene-borane 5b
analogously to the 3a/4a/5a conversion. Yield: 25%; 31P NMR
d
0.07e1.13 (m, 3H, BH3), 0.91 (d, J ¼ 6.6, 6H, CH(CH3)2), 1.32e1.45
(CDCl3)
d
32.9 (broad); 13C NMR (CDCl3)
d
19.1 (3JPeC ¼ 7.6, C3eCH3),
(m, 2H, CH2CH2CH), 1.52e1.70 (m, 3H, PCH2 and CHMe2), 1.81 (bs,
3H, C3eCH3), 2.30e2.62 (m, 4H, CH2PCH2), 5.44 (d, J ¼ 21.2, 1H,
24.37 (3JPeC ¼ 7.9) and 24.39 (3JPeC ¼ 7.9) CH(CH3)2, 25.0 (CHMe2),
31.5 (1JPeC ¼ 34.5, C5), 35.1 (1JPeC ¼ 28.3, PCH2), 35.4 (1JPeC ¼ 36.2,
CH¼); HRMS [M þ Na]þ
¼ 207.1452, C10H22PBNa requires
found
C2), 121.7 (C4), 137.7 (2JPeC ¼ 2.9, C3); 1H NMR (CDCl3)
d 0.30e0.90
207.1450 for the 11B isotope.
(m, 3H, BH3), 1.00 (d, J ¼ 6.7, 3H) and 1.01 (d, J ¼ 6.7, 3H) CH(CH3)2,
1.61e1.64 (m, 2H, PCH2), 1.77 (bs, 3H, C3eCH3), 2.00e2.10 (m, 1H,
CHMe2), 2.32e2.59 (m, 4H, CH2PCH2), 5.40 (d, J ¼ 21.7, 1H, CH¼);
The optically active (R)-1-isopentyl-3-methyl-3-phospholene-
borane ((R)-5c) was prepared analogously from (S)-1-isopentyl-3-
methyl-3-phospholene-1-oxide ((S)-3c) with an ee of 95%. Yield of
HRMS [M þ Na]þ
¼ 193.1297, C9H20PBNa requires 193.1293 for
found
(R)-5c: 30%; ½a 2D5
ꢃ
¼ ꢀ2.1 [c 1.4, CHCl3]; 31P NMR (CDCl3)
d 33.3
the 11B isotope.
(broad); 13C NMR (CDCl3)
d
19.2 (3JPeC ¼ 7.7), 22.2, 23.5 (1JPeC ¼ 30.7),
The optically active (S)-1-isobutyl-3-methyl-3-phospholene-
borane ((S)-5b) was prepared analogously from (R)-1-isobutyl-3-
methyl-3-phospholene-1-oxide ((R)-3b) with an ee of 96%. Yield of
29.3 (3JPeC ¼ 12.1), 30.1 (1JPeC ¼ 34.1), 31.8 (2JPeC ¼ 2.1), 33.9
(1JPeC ¼ 35.8),122.0,138.0 (2JPeC ¼ 2.6); 1H NMR (CDCl3)
d 0.30e0.72
(m, 3H), 0.91 (d, J ¼ 6.6, 6H), 1.36e1.43 (m, 2H), 1.54e1.68 (m, 3H),
1.81 (bs, 3H), 2.29e2.60 (m, 4H), 5.43 (d, J ¼ 20.8, 1H); MS m/z:
[M þ Na]þ ¼ 207.
(S)-5b:32%;½a 2D5
ꢃ
¼ ꢀ0.7[c1.3,CHCl3];31PNMR(CDCl3)
d31.4(broad);
13C NMR (CDCl3)
d
19.2 (3JPeC ¼ 7.6), 24.34 (3JPeC ¼ 7.9), 24.47
(3JPeC ¼ 7.9), 25.1, 31.6 (1JPeC ¼ 34.5), 35.2 (1JPeC ¼ 28.3), 35.5
(1JPeC ¼ 35.5), 121.8, 137.8 (2JPeC ¼ 2.9); 1H NMR (CDCl3)
d 0.32e0.89
(m, 3H), 1.01 and 1.02 (d, J ¼ 6.7, 6H), 1.62e1.66 (m, 2H), 1.79 (bs, 3H),
4.12. Preparation of cis-[bis(1-isopentyl-3-methyl-3-phospholeno)-
dichloro-platinum(II)] (6c)
2.02e2.12 (m, 1H), 2.33e2.61 (m, 4H), 5.41 (d, J¼21.7, 1H); HRMS
[MþNa]þ
¼ 193.1298, C9H20PBNa requires 193.1293 for the 11B
found
isotope.
Racemic 1-isopentyl-3-methyl-3-phospholene-1-oxide (3c)
(0.11 g (0.58 mmol)) was transformed to complex 6c analogously to
the 3a / 4a / 6a conversion. Yield: 97% as a 1:1 mixture of homo-
((R,R) and (S,S)) and the heterochiral (R,S) forms on the basis of the
4.10. Preparation of cis-[bis(1-isobutyl-3-methyl-3-phospholeno)-
dichloro-platinum(II)] (6b)
13C NMR data; 31P NMR (CDCl3)
d
16.3 (JPteP ¼ 3452); 13C NMR
Racemic 1-isobutyl-3-methyl-3-phospholene-1-oxide (3b)
(0.10 g (0.58 mmol)) was transformed to complex 6b analogously to
the 3a / 4a / 6a conversion. Yield: 62% as a 3*:1* mixture of
(CDCl3) d 18.9e19.0 (m, C3eCH3), 22.1e22.2 (m, CH(CH3)2), 26.0
(2JPteC ¼ 35, 1JPeC ¼ 43, 3JPeC ¼ 7, PCH2), 28.9 (4JPteC ¼ 37, 3JPeC ¼ 7,
5JPeC ¼ 7, CHMe2), 31.8e33.1 (m, C5), 33.2 (3JPteC ¼ 24, CH2CH2CH),
35.6e36.8 (m, C2), 122.0e122.5 (m, C4), 138.3e138.9 (m, C3); 1H
*
homo- ((R,R) and (S,S)) and the heterochiral (R,S) forms, may be
reversed; 31P NMR (CDCl3)
d
14.19 (JPteP ¼ 3450, 75%), 14.20
NMR (CDCl3)
d
0.91 (d, J ¼ 6.5, 6H, CH(CH3)2), 1.38e1.58 (m, 2H,
(JPteP ¼ 3449, 25%); 13C NMR (CDCl3)
d
18.9e19.1 (m, C3eCH3),
CH2CH2CH), 1.60e1.72 (m, 1H, CHMe2), 1.84 (bs, 3H, C3eCH3), 1.89e
2.10 (m, 2H, PCH2), 2.73e3.08 (m, 4H, CH2PCH2), 5.52 (d, J ¼ 24.9,
24.6e25.1 (m, CH(CH3)2), 25.7 (3JPteC ¼ 17, CHMe2), 32.9e34.2 (m,
PCH2), 36.4e37.9 (m, C2 and C5), 121.8e122.5 (m, C4), 138.5e139.1
1H, CH]); HRMS [M ꢀ Cl]þ
¼ 569.1785, C20H38P2ClPt requires
found
(m, C3); 1H NMR (CDCl3)
d
1.13e1.18 (m, 6H, CH(CH3)2), 1.84 (bs, 3H,
569.1784 for the 35Cl and 195Pt isotopes.