Olefin Metathesis
3931±3950
1
114.2 (s, CH2), 34.0 (s, CH2CH ), 31.3 (d, J(C,P) 11 Hz, PCH2),[57] 29.0
for C36H35F3NO4P2SRe (882.88): C 49.98, H 4.11, N 1.59; found: C 50.10, H
4.21, N 1.49.
(s, 2 Â intensity, CH2CH2CH2CH CH2), 28.5 (d, 3J(C,P) 11 Hz,
5
PCH2CH2CH2), 26.1 (d, 2J(C,P) 15 Hz, PCH2CH2); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d 23.8 (s); MS (FAB, 3-NBA/CH2Cl2): m/z
[(h -C5H5)Re(NO)(PPh3)(P(Me)CH2CH CHCH2)]
TfO
(11a):
A
Schlenk flask was charged with 10a (0.204 g, 0.249 mmol) and CH2Cl2
(150 mL). Solid 1 (0.016 g, 0.017 mmol, 8 mol%) was added in four
portions over 1 h with stirring. After another hour, the mixture was filtered
through a silica plug. Solvent was removed from the filtrate by oil pump
vacuum. Column chromatography (silica gel, 10 Â 2 cm, 95:5 v/v CH2Cl2/
methanol) gave a yellow eluate which was dried by oil pump vacuum to
give 11a as a yellow foam (0.193 g, 0.244 mmol, 96%). M.p. 768C; 1H NMR
(400 MHz, CDCl3, 328C, TMS): d 7.55 ± 7.26 (m, 15H, 3Ph), 5.78 (m, 2H,
(%): 331 (100) [M] ; elemental analysis calcd (%) for C22H35P (330.49): C
79.95, 10.67; found: C 79.95, H 9.90.
5
[(h -C5Me5)Re(NO)(PPh((CH2)6CH CH2)2)(CO)] BF4 (14): A Schlenk
flask was charged with [(h5-C5Me5)Re(NO)(NCMe)(CO)] BF4 (0.190 g,
0.374 mmol), 13 (0.103 g, 0.312 mmol), and ClCH2CH2Cl (20 mL), and fitted
with a condenser. The solution was heated under reflux (15 h). Solvent was
removed by oil pump vacuum. Column chromatography (silica gel, 20 Â
2 cm, CH2Cl2) gave a red by-product band. The eluent was changed to 97:3
v/v CH2Cl2/methanol (yellow band containing some 14) and then 92:8 v/v
CH2Cl2/methanol. Solvent was removed from the last series of fractions by
oil pump vacuum to give spectroscopically pure 14 (0.101 g, 0.127 mmol,
41%). An analytical sample was obtained by further column chromatog-
raphy (silica gel, 7:3 v/v CH2Cl2/acetone). 1H NMR (400 MHz, CDCl3,
CH CH), 5.56 (s, 5H, C5H5), 2.63 (m, 3H of PCHH' PC'HH'), 2.17 (m,
1H of PCHH' PC'HH'), 1.62 (d, 2J(H,P) 10 Hz, 3H, PCH3); 13C{1H}
NMR (100 MHz, CDCl3, 328C, TMS): d 133.9 (d, 1J(C,P) 56 Hz, i-Ph),
133.2 (d, 2J(C,P) 11 Hz, o-Ph), 131.6 (d, 4J(C,P) 1 Hz, p-Ph), 129.3 (d,
3
J(C,P) 11 Hz, m-Ph), 128.9 (s, CH ), 128.3 (s, C'H ), 91.9 (s, C5H5), 38.8
(d, 1J(C,P) 35 Hz, PCH2), 35.3 (d, 1J(C,P) 33 Hz, PC'H2), 17.4 (d,
1J(C,P) 34 Hz, PCH3); 31P{1H} NMR (161 MHz, CDCl3, 328C): d 13.8
(d, 2J(P,P) 14 Hz, PPh3), 15.8 (d, 2J(P,P) 14 Hz, PMeR2); IR (KBr):
328C, TMS): d 7.56 ± 7.45 (m, 5H, Ph), 5.74 (m, 2H, 2CH ), 4.92 (m, 4H,
2
CH2), 2.37 (m, 4H, 2PCH2), 2.01 (m, 4H, 2CH2CH ), 1.93 (s, 15H,
nÄ 1695 (NO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 644 (100) [M]
C5(CH3)5), 1.45 ± 1.25 (m, 16H, 8CH2); 13C{1H} NMR (100 MHz, [D6]ben-
2
of cation; elemental analysis calcd (%) for C29H29F3NO4P2SRe (792.77): C
43.94, H 3.69, N 1.77; found: C 44.33, H 3.97, N 1.46.
zene, 328C): d 203.8 (d, J(C,P) 8 Hz, ReCO), 139.0 (s, CH ), 131.7 (d,
1J(C,P) 53 Hz, i-Ph,), 129.9 (d, 2J(C,P) 11 Hz, o-Ph), 128.6 (d, 3J(C,P)
5
10 Hz, m-Ph), 127.8 (s, p-Ph), 114.5 (s, CH2), 106.1 (s, C5(CH3)5), 34.0 (s,
[(h -C5H5)Re(NO)(PPh3)(P(Ph)CH2CH CHCH2)] TfO (11b): Com-
plex 10b (0.100 g, 0.130 mmol), CH2Cl2 (150 mL), and solid 1 (0.006 g,
0.005 mmol, 4 mol% in two portions) were combined in a procedure
analogous to that given for 11a. An identical workup gave 11b as a yellow
foam (0.071 g, 0.083 mmol, 64%). M.p. 808C;[18] 1H NMR (400 MHz,
CH2CH ), 30.6 (d, J(C,P) 8 Hz, CH2), 30.4 (d, J(C,P) 11 Hz, CH2), 28.9
(s, 2 Â intensity, CH2), 28.8 (s, CH2), 24.0 (s, CH2), 9.7 (s, C5(CH3)5); 31P{1H}
NMR (161 MHz, CDCl3, 328C): d 0.4 (s); IR (solid film): nÄ 1984 (CO),
1722 (NO) cm 1; MS (FAB, 3-NBA/CH2Cl2): m/z (%): 710 (100) [M] of
cation; elemental analysis calcd (%) for C33H50BF4NO2PRe (796.75): C
49.75, H 6.33, N 1.76; found: C 49.81, H 6.59, N 1.73.
CDCl3, 328C, TMS): d 7.49 ± 7.02 (m, 20H, 4Ph), 5.74 (m, 2H, CH CH),
5.43 (s, 5H, C5H5), 3.11 ± 2.78 (m, 4H, 2PCH2); 13C{1H} NMR (100 MHz,
CDCl3, 328C, TMS): d 134.8 (d, 1J(C,P) 49 Hz, i-PPhR2), 133.7 (d,
1J(C,P) 56 Hz, i-PPh3), 133.1 (d, 2J(C,P) 11 Hz, o-PPh3/PPhR2), 131.6
5
[(h -C5Me5)Re(NO)(PPh((CH2)6CH CH2)2)(Cl)] (15): A Schlenk flask
was charged with 14 (0.300 g, 0.377 mmol) and THF (20 mL). Then LiAlH4
(0.047 g, 1.243 mmol) was added with stirring. After 2 h, small amounts of
water were added until gas evolution ceased. Solvent was removed by oil
pump vacuum. Then CH2Cl2 (ca. 20 mL) was added, and the sample
filtered. Aqueous HCl (12n; 0.20 mL, 2.4 mmol) was added with stirring.
After 0.5 h, the sample was concentrated and filtered through a silica plug
(3 cm). Solvent was removed from the filtrate by oil pump vacuum to give
15 as dark red solid (152 mg, 0.213 mmol, 56%). M.p. 162 1748C;
1H NMR (400 MHz, CDCl3, 328C, TMS): d 7.72 ± 7.63 (m, 2H of Ph),
(d, 4J(C,P) 2 Hz, p-PPh3), 130.8 (s, p-PPhR2), 129.8 (d, 3J(C,P) 10 Hz,
3
m-PPh3), 129.2 (d, J(C,P) 10 Hz, m-PPhR2), 129.1 (s, CH ), 129.0 (s,
C'H ), 92.5 (s, C5H5), 39.9 (d, 1J(C,P) 34 Hz, PCH2), 34.6 (d, 1J(C,P)
33 Hz, PC'H2); 31P{1H} NMR (161 MHz, CDCl3, 328C): d 11.7 (d,
2J(P,P) 12 Hz, PPh3), 1.4 (d, 2J(P,P) 12 Hz, PPhR2); IR (solid film):
nÄ 1695 (NO) cm 1; MS (FAB, 3-NBA): m/z (%): 706 (100) [M] of cation.
PPh2(CH2)6CH CH2 (12):[21] A Schlenk flask was charged with PPh2H
(3.210 g, 17.24 mmol) and THF (90 mL). Then nBuLi (2.5m in hexanes;
7.2 mL, 18 mmol) was added dropwise with stirring. The solution turned
orange-red.[20a] After 10 min, a solution of 4 (3.130 g, 16.38 mmol) in THF
(10 mL) was added. The sample turned light yellow. After 3 h, solvent was
removed by oil pump vacuum to give a white solid suspended in an oil.
Hexane (30 mL) was added, and the mixture was passed through a silica
plug (2 cm). Solvent was removed by oil pump vacuum. The residue was
distilled under vacuum to give 12 as a viscous colorless liquid (4.515 g,
15.23 mmol, 88%). Procedures using KPPh2 (Fluka, 0.5m in THF) gave
equivalent results. 1H NMR (300 MHz, CDCl3, 208C): d 7.45 ± 7.32 (m,
7.15 ± 7.00 (m, 3H of Ph), 5.83 ± 5.66 (m, 2H, 2CH ), 5.06 ± 4.92 (m, 4H,
2
CH2), 2.76 ± 2.38 (m, 4H, 2PCH2), 2.00 ± 1.84 (m, 4H, 2CH2CH ), 1.53
(s, 15H, C5(CH3)5), 1.37 ± 1.00 (m, 16H, 8CH2); 13C{1H} NMR (100 MHz,
2
CDCl3, 328C, TMS): d 139.0 (s, CH ), 131.7 (d, J(C,P) 12 Hz, o-Ph),
131.1 (partially obscuredd, 1J(C,P) 50 ± 56 Hz, i-Ph), 129.7 (s, p-Ph), 128.7
3
(d, J(C,P) 11 Hz, m-Ph), 114.6 (s, CH2), 99.4 (s, C5(CH3)5), 34.0 (s,
CH2CH ), 31.3 (d, J(C,P) 13 Hz, CH2), 29.1 (d, J(C,P) 9 Hz, CH2), 28.8
(s, CH2), 26.3 (s, CH2), 23.2 (s, CH2), 10.1 (s, C5(CH3)5); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d 6.9 (s); IR (solid film): nÄ 1637
(NO) cm 1; MS (FAB, 3-NBA): m/z (%): 717 (100) [M] ; elemental
10H, 2Ph), 5.79 (m, 1H, CH ), 5.02 ± 4.91 (m, 2H, CH2), 2.07 ± 1.99 (m,
4H, CH2CH PCH2), 1.45 ± 1.27 (m, 8H, 4CH2); 13C{1H} NMR (75 MHz,
analysis calcd (%) for C32H50ClNOPRe (717.38): C 53.58, H 7.02, N 1.95;
found: C 53.40, H 6.81, N 1.59.
1
CDCl3, 208C): d 139.3 (s, CH ), 139.2 (d, J(C,P) 16 Hz, i-Ph), 132.9 (d,
2J(C,P) 19 Hz, o-Ph), 128.6 (d, 3J(C,P) 9 Hz, m-Ph), 128.6 (s, p-Ph),
5
[(h -C5Me5)Re(NO)(P(Ph)(CH2)6CH CH(CH2)6)(CO)] BF4 (16):
A
114.4 (s, CH2), 34.0 (s, CH2CH ), 31.3 (d, J(C,P) 13 Hz, PCH2),[57] 29.0
1
Schlenk flask was charged with 14 (0.150 g, 0.188 mmol), CH2Cl2
(150 mL) and 1 (0.0064 g, 0.0078 mmol, 4 mol%). The sample was stirred
for 14 h, and filtered through a Celite plug (2 cm). Solvent was removed by
oil pump vacuum to give 16 as a dark solid of >98% spectroscopic purity
(0.142 g, 0.178 mmol, 94%; Z/E (tentative)[23] 44:56[55b,c]). Extensive
attempts to obtain analytically pure samples were unsuccessful. M.p.
688C;[18] 1H NMR (400 MHz, CDCl3, 328C, TMS): d 7.56 ± 7.45 (m, 5H,
(s, 2 Â intensity, CH2CH2CH2CH CH2), 28.2 (d, 3J(C,P) 11 Hz,
PCH2CH2CH2), 26.1 (d, 2J(C,P) 16 Hz, PCH2CH2); 31P{1H} NMR
(161 MHz, CDCl3, 328C): d 15.8 (s); elemental analysis calcd (%) for
C20H25P (296.39): C 81.05, 8.50; found: C 81.02, H 8.44.
PPh((CH2)6CH CH2)2 (13):[21] A Schlenk flask was charged with PPhH2
(0.938 g, 8.52 mmol) and THF (40 mL) and was cooled to 08C. Then nBuLi
(1.8m in hexanes, 10.1 mL, 18 mmol) was added dropwise with stirring over
10 min.[20b] After another 10 min, a solution of 4 (3.260 g, 17.06 mmol) in
THF (5 mL) was added. The cold bath was removed. After 2 h, solvent was
removed by oil pump vacuum. The residue was filtered through a silica plug
(3 cm) with hexane (3 Â 20 mL). The filtrate was taken to dryness by oil
pump vacuum. The residue was distilled (10 2 bar, 111 ± 1158C) to give 13
Ph), 5.42 ± 5.38/5.36 ± 5.26 (2m, 2H, E/Z CH CH, 56:44), 2.43 (m, 4H,
2PCH2), 2.10 (m, 4H, 2CH2CH ), 1.97/1.96 (2s, 15H, C5(CH3)5), 1.50 ± 1.21
(m, 16H, 8CH2); 13C{1H} NMR (100 MHz, CDCl3, 328C, TMS): d 203.7
(brs, ReCO) 137.3/137.0 (2s, CH ), 134.7 ± 126.8 (PPh signals), 99.1/99.0
(2s, C5(CH3)5), 36.0/35.4 (2s, CH2CH ), 32.9 ± 21.9 (CH2 signals), 10.1/10.0
(2s, C5(CH3)5); 31P{1H} NMR (161 MHz, CDCl3, 328C): d 0.71/ 0.85
(2s, Z/E, 44:56); IR (solid film): nÄ 1980 (CO), 1718 (NO) cm 1; MS (FAB,
as
a
viscous colorless liquid (2.200 g, 6.657 mmol, 78%). 1H NMR
(400 MHz, CDCl3, 328C): d 7.63 (m, 1H of Ph), 7.49 (m, 2H of Ph),
3-NBA/CH2Cl2): m/z (%): 682 (100) [M] of cation.
7.34 (m, 2H of Ph), 5.79 (m, 2H, 2CH ), 4.90 (m, 4H, 2 CH2), 1.98 (m, 4H,
5
[(h -C5Me5)Re(NO)(P(Ph)(CH2)6CH CH(CH2)6)(Cl)] (17)
2CH2CH ), 1.69 (m, 4H, 2PCH2), 1.42 ± 1.08 (m, 16H, 8CH2); 13C{1H}
NMR (100 MHz, CDCl3, 328C): d 139.4 (m, i-Ph), 139.1 (s, CH ), 132.6
A: A Schlenk flask was charged with 15 (0.074 g, 0.105 mmol), 1 (0.0042 g,
0.0051 mmol, 5 mol%), and CH2Cl2 (150 mL). The sample was stirred for
(d, 2J(C,P) 18 Hz, o-Ph), 128.2 (d, 3J(C,P) 20 Hz, m-Ph), 128.4 (s, p-Ph),
Chem. Eur. J. 2001, 7, No. 18
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
0947-6539/01/0718-3943 $ 17.50+.50/0
3943