Transformation of an FePdC Unit of a Phosphaalkene
Organometallics, Vol. 16, No. 13, 1997 2959
dichloromethane to the slurry was accompanied by efferves-
cence and a color change from dark red to orange. Stirring
was continued for 24 h at 20 °C. Volatile compounds were
removed in vacuo, and the remaining red-brown powder was
extracted with 40 mL of ether. The extract was freed from
the solvent to yield 3b as a red-brown powder (1.41 g, 66%).
Attempts to crystallize the compound invariably led to decom-
position. IR (Nujol, cm-1): ν 1982 vs [ν(CO)], 1934 vs [ν(CO)],
1560 w, 1500 m, 1310 w, 1291 m, 1264 m, 1227 m, 1151 w,
1097 w, 930 w, 844 w, 642 w, 580 m. 1H NMR: δ 1.53 (s,
15H, C5Me5), 2.40 (s, 6H, NCH3), 2.67 (s, 6H, NCH3), 7.15 (m,
Sch em e 2
2
4H, aryl H), 9.14 (d, J PH ) 9.0 Hz, PdCH). 13C{1H} NMR: δ
9.36 [s, C5(CH3)5], 38.8 (s, NCH3), 39.2 (s, NCH3), 95.7 [s, C5-
(CH3)5], 114.3 s, 115.6 s, 115.8 s, 144.8 (s, aryl C), 165.8 (s,
1
C)N), 175.1 (d, J PC ) 69.2 Hz, PdC), 219.0 (s, CO). 31P{1H}
NMR: δ 204.4 s. 19F{1H} NMR: δ 97.4 s. MS/CI: m/z 514
(M+), 458 (M+ - 2CO). Anal. Calcd for C24H32FFeN4O2P
(514.36): C, 56.04; H, 6.27; N, 10.89. Found: C, 54.80; H, 5.98;
N, 10.30. Various attempts at purification were unsuccessful
due to partial decomposition to (η5-C5Me5)2Fe2(CO)4 and
unidentified components.
(E)-(η5-C5Me5)(CO)2F eP dCH N(4-ClC6H 4)NdC(NMe2)2
(3c). Similarly, compound 1 (0.80 g, 2.12 mmol) and 3-(p-
chlorophenyl)sydnone 2c (0.43 g, 2.12 mmol) were reacted in
a mixture of ether (30 mL) and dichloromethane (10 mL) at
0-10 °C. After 2 h of stirring the solution was evaporated to
dryness, and the red-brown solid residue was extracted with
ether (40 mL). Filtration of the extract and removal of solvent
in vacuo yielded 3c as a red-brown powder (0.81 g, 72%). IR
(Nujol, cm-1): ν 1983 vs [ν(CO)], 1934 vs [ν(CO)], 1758 w, 1665
w, 1589 w, 1557 w, 1485 s, 1307 w, 1287 m, 1263 m, 1222 w,
1151 w, 1093 w, 817 m, 797 w, 641 w, 582 m. 1H NMR: δ
1.52 (s, 15H, C5Me5), 2.38 (s, 6H, NCH3), 2.66 (s, 6H, NCH3),
7.00-7.14 (m, 4H, aryl H), 9.16 (d, 2J PH ) 9.2 Hz, PdCH). 13C-
{1H} NMR: δ 9.34 [s, C5(CH3)5], 38.5 (s, NCH3), 39.2 (s, NCH3),
95.8 [s, C5(CH3)5], 115.6 s, 129.1 s, 144.4 (s, aryl C), 165.9 (s,
1
CdN), 174.5 (d, J PC ) 67.7 Hz, PdC), 218.8 (s, CO). 31P{1H}
P r ep a r a t ion of Com p ou n d s. (E)-(η5-C5Me5)(CO)2-
F eP dCHN(P h )NdC(NMe2)2 (3a ). A sample of solid 3-phen-
ylsydnone 2a (0.50 g, 3.06 mmol) was added to a solution of
(η5-C5Me5)(CO)2FePdC(NMe2)2 (1) in diethyl ether (40 mL).
In order to obtain a homogeneous solution, dichloromethane
(10 mL) was added at ambient temperature, whereupon an
effervescence and a color change from dark red to orange-red
was observed. After the mixture was stirred overnight, solvent
and volatiles were removed in vacuo. The remaining red-
brown powder was extracted with ether (40 mL) and filtered.
The filtrate was stored at -30 °C for 24 h to yield dark red
diamond-shaped crystals. Concentration of the mother liquor
to ca. 10 mL and repeated crystallization furnished a second
crop of 3a . Yield: 0.93 g (61%). IR (Nujol, cm-1): ν 1985 vs
[ν(CO)], 1940 s [ν(CO)], 1589 s [ν(CN)], 1551 s, 1490 s, 1422
w, 1365 s, 1305 m, 1264 m, 1218 w, 1176 w, 1151 m, 1137 w,
1105 m, 1074 w, 1063 w, 1041 w, 1027 w, 991 m, 930 m, 899
w, 874 w, 817 m, 776 w, 763 m, 746 s, 690 m, 640 m, 630 m,
578 s, 548 s, 510 m. 1H NMR: δ 1.69 (s, 15H, C5Me5), 2.59 (s,
6H, NCH3), 2.85 (s, 6H, NCH3), 6.86-7.53 (s, br, 5H, C6H5),
NMR: δ 215.4 s. MS/CI: m/z 530 (M+), 502 (M+ - CO), 474
(M+ - 2CO). Anal. Calcd for C24H32ClFeN4O2P (580.82): C,
54.30; H, 6.07; N, 10.56. Found C, 54.43; H, 6.12; N, 10.15.
(E)-(η5-C5Me5)(CO)2F eP dCH N(4-Br C6H 4)NdC(NMe2)2
(3d ). Analogously, equimolar amounts of 1 (1.76 g, 4.65 mmol)
and 3-(p-bromophenyl)sydnone 2d (1.20 g, 4.65 mmol) were
reacted in a mixture of ether (40 mL) and dichloromethane
(10 mL) in the temperature range of 0-10 °C. Workup as
described above afforded 1.79 g (67%) of 3d as a red-brown
powder. IR (Nujol, cm-1): ν 1983 vs [ν(CO)], 1934 vs [ν(CO)],
1583 w, 1481 m, 1262 w, 1148 m, 1073 w, 1031 m, 973 w, 815
m, 801 w, 642 w, 582 m. 1H NMR: δ 1.53 (s, 15H, C5Me5),
2.39 (s, 6H, NCH3), 2.67 (s, 6H, NCH3), 7.10-7.44 (m, 4H, aryl
2
H), 9.14 (d, J PH ) 9.4 Hz, PdCH). 13C{1H} NMR: δ 9.30 [s,
C5(CH3)5], 38.5 (s, NCH3), 39.2 (s, NCH3), 95.8 [s, C5(CH3)5],
116.2 s, 131.9 s, 144.8 (s, aryl C), 165.9 (s, CdN), 174.5 (d,
1J PC ) 68.3 Hz, PdC), 218.8 (s, CO). 31P{1H} NMR: δ 216.7
s. MS/CI: m/z ) 576 (M+ + H), 548 (M+ + H - CO), 520 (M+
+ H - 2CO). Anal. Calcd for C24H32BrFeN4O2P (575.27): C,
50.11; H, 5.61; N, 9.74. Found C, 49.35; H, 5.63; N, 9.22.
Various attempts at purification were unsuccessful due to
partial decomposition.
2
9.41 (d, J PH ) 8.8 Hz, PCH). 13C{1H} NMR: δ 10.1 [s, C5-
(CH3)5], 39.4 (s, NCH3), 40.0 (s, NCH3), 94.6 [s, C5(CH3)5], 115.6
s, 121.1 s, 129.9 s, 146.9 (s, phenyl C), 166.6 (s, CdN), 176.0
(d, 1J PC ) 69.2 Hz, PdC), 219.7 (s, CO). 31P{1H} NMR: δ 204.9
s. MS/CI: m/z ) 496 (M+), 440 (M+ - 2CO), 397 (M+ - 2CO
- MeNdCH2). Anal. Calcd for C24H33FeN4O2P (496.36): C,
58.07; H, 6.70; N, 11.29. Found: C, 57.95; H, 6.88; N, 11.19.
(E)-(η5-C5Me 5)(CO)2F eP dCH N(4-F C6H 4)NdC(NMe 2)2
(3b). A sample of solid 3-(fluorophenyl)sydnone 2b (0.74 g,
4.15 mmol) was added to a chilled solution (0 °C) of 1 (1.57 g,
4.15 mmol) in 50 mL of ether. The addition of 10 mL of
R ea ct ion
of
E -(η5-C5Me5)(CO)2F eP dCH N(P h )Nd
C(NMe2)2 (3a ) w ith Dim eth yl F u m a r a te. A solution of 0.25
g (1.73 mmol) of dimethyl fumarate in 10 mL of ether was
added over 30 min to the chilled solution (-30 °C) of 0.86 g
(1.73 mmol) of 3a in 50 mL of ether. After it was warmed to
ambient temperature, the orange solution was stirred for 24
h. Filtration was followed by evaporation of the filtrate to
dryness. The solid residue was dissolved in 25 mL of ether
and stored at 5 °C for 24 h to yield 0.69 g (63%) of orange
crystalline 4a . IR (Nujol, cm-1): ν 1997 vs [ν(CO)], 1939 vs
[ν(CO)], 1723 vs [ν(CO)ester], 1595 m, 1579 m, 1560 m, 1506 m,
1484 w, 1435 w, 1351 w, 1313 w, 1263 w, 1209 m, 1157 w,
1120 w, 1065 w, 1035 w, 993 w, 953 w, 918 w, 754 w, 699 w,
(14) Baker, W.; Ollis, W. D.; Poole, V. D. J . Chem. Soc. 1949,
307.
(15) Eade, R. A.; Earl, J . C. J . Chem. Soc. 1948, 2307.
(16) Eade, R. A.; Earl, J . C. J . Chem. Soc. 1946, 591.
(17) Hammick, D. L.; Voaden, D. J . J . Chem. Soc. 1961, 3303.