N. Hoffmann, C. Wismach, L. Ernst, H. Schiebel, P. G. Jones, R. Streubel
FULL PAPER
1
Yield: 620 mg, 77%; m.p. 87 °C (decomp.). H NMR: δ ϭ 0.83 (d,
J ϭ 15.0 Hz, 3 H, cp*-1-Me), 1.25 (br. s, 3 H, cp*-5-Me), 1.52 (br.
199.8 (d, J ϭ 23.6 Hz, WCO-trans) ppm. 31P NMR: δ ϭ 18.5 (d,
J ϭ1.3 Hz, PPh3), 97.0 [d, J ϭ1.3, J(183W, P ) ϭ 242.6 Hz, PW] ppm.
s, 3 H, cp*-2-Me), 1.660 (dd, J ϭ 4.2, 1.2 Hz, 3 H, cp*-4-Me), UV/Vis (CH3CN): λ (lg ε) ϭ 230 (4.89), 258 (4.48), 272 (4.30), 284
1.673 (dd, J ϭ 4.3, 1.2 Hz, 3 H, cp*-3-Me), 3.74 (s, 3 H, 4- or 3-
azaphosphole(azap)-COOMe), 3.94 (s, 3 H, 3- or 4-azap-COOMe),
(4.17), 296 (4.10), 316 (3.89), 340 (3.65), 360 (3.39) nm. IR (KBr):
ν˜ ϭ 2079 (vs, CO), 1988 (vs, CO), 1939 (s, CO), 1735 (vs, CO2),
7.44 (mc, 6 H, H-meta of PPh3), 7.55 (mc, 3 H, H-para of PPh3), 1724 (vs, CO2) cmϪ1. MS (EI, 184W): m/z ϭ 1076 (7) [M]ϩ·, 752
7.80 (m, 6 H, H-ortho of PPh3) ppm. 13C NMR: δ ϭ 11.16 (d, J ϭ (30) [M Ϫ W(CO)5]ϩ·, 277 (100) [Nor.]ϩ, 262 (78) [PPh3]ϩ·, 183
1.5 Hz, cp*-4-Me), 11.22 (d, J ϭ 0.7 Hz, cp*-5-Me), 11.4 (d, J ϭ (55) [PPh2]ϩ. C46H42N2O13P2W (1076.6): calcd. C 51.32, H 3.93, N
1.5 Hz, cp*-3-Me), 12.2 (d, J ϭ 1.6 Hz, cp*-2-Me), 13.7 (d, J ϭ 2.60; found C 49.77, H 4.04, N 2.54.
0.9 Hz, cp*-1-Me), 52.1 (s, azap-4- or 3-COOMe), 52.5 (s, azap-3-
or 4-COOMe), 62.6 (dd, J ϭ 6.1, 0.5 Hz, cp*-C-1), 127.3 (d, J ϭ
[Pentacarbonyl{4,5,8,9-tetrakis(methoxycarbonyl)-2,3,6,7,12-penta-
methyl-10-triphenylphosphonioiminoyl-1-aza-11-phos-
100.7 Hz, C-ipso of PPh3), 128.7 (d, J ϭ 12.5 Hz, C-meta of PPh3),
phatetracyclo[6.2.1.13,6.02,7]dodeca-4,9-diene-κP}tungsten(0)]
132.5 (d, J ϭ 2.9 Hz, C-para of PPh3), 133.4 (d, J ϭ 10.1 Hz, C-
(13): 12 (0.37 g, 0.00034 mol) was dissolved in o-xylene (1.8 mL)
ortho of PPh3), 137.1 (s, cp*-C-5), 137.2 (d, J ϭ 3.0 Hz, cp*-C-2),
and heated at 120 °C for 100 min while stirring slowly. All volatile
components were then removed in vacuo (ca. 0.01 mbar) and the
products separated by low-temperature column chromatography
(SiO2, Ϫ10 °C, 10 ϫ 2 cm, n-pentane/diethyl ether, 10:30). Evapor-
ation of the second fraction and recrystallization from diethyl ether
yielded complex 13 as pale a yellow solid.
139.4 (d, J ϭ 6.7 Hz, cp*-C-3), 140.0 (d, J ϭ 5.9 Hz, cp*-C-4),
149.4 (dd, J ϭ 26.1, 18.9 Hz, azap-C-4), 151.6 (dd, J ϭ 4.4, 2.7 Hz,
azap-C-3), 163.8 (dd, J ϭ 10.7, 2.3 Hz, azap-4- or 3-COOMe),
165.4 (dd, J ϭ 14.5, 1.0 Hz, azap-3- or 4-COOMe), 166.5 (dd, J ϭ
11.7, 5.5 Hz, azap-C-5), 196.5 (d, J ϭ 7.4, J(183W, C ) ϭ 126.5 Hz,
WCO-cis), 199.5 (d, J ϭ 25.4 Hz, WCO-trans) ppm. 31P NMR: δ ϭ
18.1 (d, J ϭ 1.2 Hz, PPh3), 105.0 [br. s, J(183W, P ) ϭ 256.0 Hz, azap-
P] ppm. UV/Vis (CH3CN): λ (lg ε) ϭ 228 (4.90), 248 (4.64), 274
(4.15), 300 (3.86), 324 (3.84), 360 (3.71), 380 (3.52) nm. IR (KBr):
ν˜ ϭ 2069 (vs, CO), 1980 (vs, CO), 1931 (s, CO), 1741 (vs, CO2),
1719 (vs, CO2) cmϪ1. MS (EI, 184W): m/z ϭ 934 (1) [M]ϩ·, 903 (1)
[M Ϫ OCH3]ϩ, 799 (100) [M Ϫ Cp*]ϩ·, 771 (18) [M Ϫ Cp*-CO]ϩ·
743 (45) [M Ϫ Cp*-2CO]ϩ·, 687 (40) [M Ϫ Cp*-4CO]ϩ·, 659 (90)
,
[M Ϫ Cp*-5CO]ϩ·, 631 (35) [M Ϫ Cp*-6CO]ϩ·, 262 (20) [PPh3]ϩ·
,
183 (30) [PPh2]ϩ. C40H36N2O9P2W (934.5): calcd. C 51.41, H 3.88,
N 3.00; found C 51.26, H 4.23, N 3.20.
{Pentacarbonyl[2,3-bis(methoxycarbonyl)-2-(1,4,5,6,7-pentamethyl-
norborna-2,5-dien-7-yl)-3,4-bis(methoxycarbonyl)-5-(N-tri-
phenylphosphonioiminoyl)-2H-1,2-azaphosphole-κP]tungsten(0)}
(12): Carbonitrile 10 (1 mmol) and DMAD (2 mmol) were added
to a toluene (6 mL) solution of 2H-azaphosphirene complex 11
(0.6 g, 1 mmol). The solution was heated at 75 °C for 20 h while
stirring slowly and was controlled by 31P NMR spectroscopy. All
Yield: 200 mg, 53%; m.p. 142 °C (decomp.). 1H NMR: δ ϭ 0.65 (s,
3 H, 3-Me), 0.74 (s, 3 H, 2-Me), 1.00 (d, J ϭ 15.4 Hz, 3 H, 12-
Me), 1.07 (s, 3 H, 6-Me), 1.35 (s, 3 H, 7-Me), 3.55 (s, 3 H, 8- or 9-
COOMe), 3.68 (s, 3 H, 4- or 5-COOMe), 3.73 (s, 3 H, 5- or 4-
COOMe), 3.74 (s, 3 H, 9- or 8-COOMe), 7.47 (mc, 6 H, H-meta of
PPh3), 7.56 (mc, 3 H, H-para of PPh3), 7.82 (m, 6 H, H-ortho of
volatile components were then removed in vacuo (ca. 0.01 mbar) PPh3) ppm. 13C NMR: δ ϭ 9.2 (d, J ϭ 14.8 Hz, 12-Me), 10.7 (s,
and the products separated by low-temperature column chromatog- 3-Me), 13.3 (v. br. s, 6-Me), 13.8 (br. d, J ϭ 4.8 Hz, 7-Me), 15.5
raphy (SiO2, Ϫ10 °C, 10 ϫ 2 cm, n-pentane/diethyl ether, 20:80). (br. d, J ϭ 4.1 Hz, 2-Me), 50.3 (s, 8- or 9-COOMe), 51.3 (d, J ϭ
Evaporation of the third fraction yielded complex 12 as a yellow
solid. Yield: 850 mg, 79%; m.p. 152 °C (decomp.). H NMR: δ ϭ
0.7 Hz, 9- or 8-COOMe), 51.96 (s, 4- or 5-COOMe), 52.02 (s, 5- or
4-COOMe), 61.4 (br. d, J ϭ 13.6 Hz, C-7), 68.6 (d, J ϭ 1.3 Hz, C-
1
0.08 [s, 3 H, norbornadiene(nor)-4-Me], 1.37 (d, J ϭ 15.7 Hz, 3 H, 3), 68.9 (s, C-6), 73.7 (d, J ϭ 13.6 Hz, C-12), 74.5 (dd, J ϭ 11.0,
nor-7-Me), 1.45 (s, 3 H, nor-5-Me), 1.49 (s, 3 H, nor-6-Me), 1.59 1.5 Hz, C-8), 85.6 (br. d, J ഠ 1.3 Hz, C-2), 98.6 (dd, J ϭ 14.1,
(s, 3 H, nor-1-Me), 3.63 (s, 3 H, 3- or 2-nor-COOMe), 3.66 (s, 3
H, 2- or 3-nor-COOMe), 3.82 [s, 3 H, 4- or 3-azaphosphole(azap)-
7.5 Hz, C-9), 128.6 (d, J ϭ 12.8 Hz, C-meta of PPh3), 130.3 (d, J ϭ
105.7 Hz, C-ipso of PPh3), 132.1 (d, J ϭ 3.0 Hz, C-para of PPh3),
COOMe], 3.98 (s, 3 H, 3- or 4-azap-COOMe), 7.46 (mc, 6 H, H- 132.9 (d, J ϭ 10.7 Hz, C-ortho of PPh3), 141.7 (d, J ϭ 4.2 Hz, C-
meta of PPh3), 7.57 (mc, 3 H, H-para of PPh3), 7.80 (mc, 6 H, H- 4), 142.6 (br. d, J ϭ 4.8 Hz, C-5), 159.8 (dd, J ϭ 4.3, 1.2 Hz, C-
ortho of PPh3) ppm. 13C NMR: δ ϭ 9.0 (s, nor-4-Me) 11.36 (d,
10), 164.8 (d, J ϭ 0.4 Hz, 5- or 4-COOMe), 165.0 (s, 4- or 5-CO-
J ϭ 4.0 Hz, nor-1-Me) 11.44 (s, nor-5-Me), 12.4 (s, nor-6-Me), 16.4 OMe), 166.1 (dd, J ϭ 5.3, 1.1 Hz, 8- or 9-COOMe), 169.3 (br. s,
(d, J ϭ 18.4 Hz, nor-7-Me), 51.6 (s, 3- or 2-nor-COOMe), 51.7 (s,
9- or 8-COOMe), 195.5 [d, J ϭ 7.8, J(183W, C ) ϭ 125.4 Hz, WCO-
2- or 3-nor-COOMe), 52.3 (s, 4- or 3-azap-COOMe), 52.5 (s, 3- or cis], 197.8 (d, J ϭ 29.9 Hz, WCO-trans) ppm. 31P NMR: δ ϭ 1.3
4-azap-COOMe), 66.0 (d, J ϭ 8.6 Hz, nor-C-1), 68.3 (d, J ϭ
4.6 Hz, nor-C-4), 90.5 (d, J ϭ 5.5 Hz, nor-C-7), 126.8 (d, J ϭ
(s, Ph3PϭN), 158.4 [s, J(183W, P ) ϭ 269.9 Hz, C2PϪN] ppm. UV/
Vis (CH3CN): λ (lg ε) ϭ 232 (4.93), 252 (4.51), 264 (4.35), 276
100.3 Hz, C-ipso of PPh3), 128.6 (d, J ϭ 12.5 Hz, C-meta of PPh3), (4.22), 300 (4.09), 318 (3.92), 332 (3.85), 356 (3.76) nm. IR (KBr):
132.5 (d, J ϭ 2.9 Hz, C-para of PPh3), 133.4 (d, J ϭ 10.1 Hz, C- ν˜ ϭ 2074 (s, CO), 1990 (s, CO), 1939 (vs, CO), 1929 (vs, CO), 1742
ortho of PPh3), 145.3 (dd, J ϭ 26.1, 19.1 Hz, ap-C-4), 146.3 (s, nor- (s, CO2), 1732 (s, CO2) cmϪ1. MS (EI, 184W): m/z ϭ 1076 (10)
C-6), 147.7 (s, nor-C-5), 149.0 (d, J ϭ 7.4 Hz, nor-C-2), 151.0 (dd,
[M]ϩ·, 934 [M Ϫ DMAD]ϩ·, 752 (15) [M Ϫ W(CO)5]ϩ·, 277 (30)
J ϭ 3.7, 2.8 Hz, azap-C-3), 156.5 (d, J ϭ 5.5 Hz, nor-C-3), 161.9 [HNPPh3]ϩ, 262 (48) [PPh3]ϩ·, 183 (46) [PPh2]ϩ, 28 (100) [CO]. MS
(dd, J ϭ 11.9, 2.3 Hz, 4- or 3-azap-COOMe), 165.1 (d, J ϭ 1.2 Hz,
2- or 3-nor-COOMe), 165.4 (dd, J ϭ 14.8, 0.9 Hz, 3- or 4-azap-
COOMe), 165.8 (dd, J ϭ 9.1, 5.7 Hz, azap-C-5), 166.0 (s, 3- or 2-
(pos.-DCI, 35Cl, 184W): m/z ϭ 1077 (22) [M ϩ H]ϩ. MS (neg.-DCI,
35Cl, 184W): ϭ m/z ϭ 1076 (12) [M]Ϫ·, 814 (38) [M Ϫ PPh3]Ϫ·
324 (62) [W(CO)5]Ϫ·. C46H42N2O13P2W (1076.6) : calcd. 1074.1644;
,
nor-COOMe), 197.2 [d, J ϭ 6.8, J(183W, C ) ϭ 127.3 Hz, WCO-cis], found 1074.1652 (δ ϭ Ϫ0.7 ppm).
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2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2003, 1815Ϫ1821