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N.J. Goodwin et al. / Inorganica Chimica Acta 295 (1999) 18–24
3.1. Synthesis of FcCH2PPh2 (3)
100 V): m/z 801 [2M+H]+, 401 [M+H]+, 335 [M−
Cp]+, 199 [FcCH2]+. 31P{1H} NMR: l 29.0 (s). 1H
NMR: l 3.42 (FcCH2P, d, J 13, 2H), 4.01 (CAꢀH and
CBꢀH, s, 4H), 4.08 (CDꢀH, s, 5H), 7.39–7.70 (Ph, m,
10H). 13C{1H} NMR: l 33.38 (FcCH2P, d, J 67), 68.02
(CA, s), 68.90 (CD, s), 69.85 (CB, s), 77.77 (CC, d, J 3),
128.43–133.06 (Ph, m).
A solution of [Ph2P(CH2OH)2]Cl (2.006 g, 7.09 mmol)
in methanol (30 ml) was purged and placed under a
nitrogen atmosphere, then KOH (0.359 g, 6.39 mmol)
was added. The solution was stirred under nitrogen for
2 h, generating a solution of Ph2PCH2OH. The
Ph2PCH2OH was added to a solution of [FcCH2NMe3]I
(2.002 g, 5.23 mmol) in methanol (40 ml) under nitro-
gen, and the resulting mixture refluxed under nitrogen
for 18 h. Most of the solvent was removed under
reduced pressure, and a mixture of water (40 ml),
diethyl ether (40 ml) and triethylamine (30 ml) added.
This mixture was stirred for 4 h, and the organic layer
isolated and filtered before washing with water (3×20
ml). Removal of solvent under reduced pressure gave an
orange oil. This was purified by tlc on silica, with
dichloromethane used to charge the plate and 10%
diethyl ether in petroleum spirits used as the eluting
solvent. The desired product ran with an Rf of 0.73, and
after removal from the plate and drying under vacuum,
3 was isolated as an orange oil which slowly crystallised
(0.505 g, 25%). M.p. 80–84°C. Found: C, 72.1; H, 5.4%.
C23H21FeP requires: C, 71.9; H, 5.5%. IR (cm−1):
1583(w), 1480(w), 1469(w), 1432(m), 1305(w), 1182(w),
1102(m), 1023(m), 999(m), 924(w), 840(w), 816(s),
741(s), 695(s), 479(s). ESMS (positive-ion, cone voltage
3.3. Synthesis of phosphonium salts 7 and 8
A small quantity (ca. 30 mg) of FcCH2PPh2 (3) was
dissolved in dichloromethane (2 ml) and an excess of
either MeI or EtI was added, and the reaction mixture
was allowed to stand overnight. The solvent was evapo-
rated, the residue washed with diethyl ether (5 ml), and
then recrystallised by diffusion of diethyl ether into a
dichloromethane solution. The resulting orange crystals
were air-dried.
7: ESMS (positive-ion, cone voltage 30 V): m/z 399
(100%), [FcCH2PPh2Me]+.
8: ESMS (positive-ion, cone voltage 30 V): m/z 413
(100%), [FcCH2PPh2Et]+.
3.4. Synthesis of [RuCl2(p6-p-cymene)(FcCH2PPh2)] (9)
The complex [RuCl2(h6-p-cymene)]2 (0.037 g, 0.0609
mmol) was dissolved in dichloromethane (10 ml), which
was placed under a nitrogen atmosphere before addition
of FcCH2PPh2 (3) (0.047 g, 0.122 mmol). The mixture
was refluxed for 15 min and the solvent removed under
reduced pressure to give the crude product as a dark oil
in quantitative yield. Recrystallisation by vapour diffu-
sion of petroleum spirits (b.p. 30–40°C) into a
dichloromethane solution at 4°C yielded the product as
large dark-purple crystals suitable for X-ray crystallo-
graphy (0.070 g, 84%). M.p.ꢀ200°C (decomp.). Found:
C, 52.6; H, 4.7%. C33H35Cl2FePRu. CH2Cl2 requires: C,
52.6; H, 4.8%. IR (cm−1): 3053(m), 2963(m), 1481(m),
1409(m), 1469(m), 1433(s), 1386(m), 1319(w), 1276(w),
1237(w), 1196(m), 1160(w), 1103(s), 1057(m), 1026(m),
1000(m), 926(m), 821(s), 750(s), 728(s), 696(s), 663(m),
597(m), 483(w). ESMS (positive-ion, cone voltage 60 V):
m/z 696 [M−Cl+MeCN]+, 384 [FcCH2PPh2]+.
20 V), m/z 384 [M]+. 31P{1H} NMR: l −11.8 (s). H
NMR: l 3.16 (FcCH2P, s, 2H), 3.92 (CBꢀH, unres. t,
1
2H), 3.98 (CAꢀH, t,
J
2, 2H), 4.10 (CDꢀH,
s, 5H), 7.31–7.42 (Ph, m, 10H). 13C{1H}: l 30.29
(FcCH2P, d, J 14), 67.42 (CA, s), 68.84 (CD, s), 69.23
(CB, d, J 4), 84.33 (CC, d, J 17), 128.35–138.85
(m, Ph).
3.2. Synthesis of FcCH2P(O)Ph2 (4)
FcCH2PPh2 (3) (0.100 g, 0.260 mmol) was placed in
a flask with hydrogen peroxide (0.190 g, 6%, 0.335
mmol), water (5 ml), methanol (35 ml) and
dichloromethane (10 ml). The solution was stirred for 1
h before most of the solvent was removed under reduced
pressure without heating. Once the product had largely
precipitated out of solution, diethyl ether was added and
the organic layer was separated and washed with water
(3×10 ml). Solvent was removed under reduced pres-
sure, giving the crude product as a yellow powder in
quantitative yield. Recrystallisation by vapour diffusion
1
31P{1H} NMR: l 28.8 (s). H NMR: l 0.86 [CH(CH3)2,
d, J 7, 6H], 1.82 (CH3, s, 3H), 2.50, [CH(CH3)2, hept.,
J 7, 1H], 3.32 (FcCH2P, s, 2H), 3.63 (CAꢀH, d, J 7, 2H),
3.70 (CBꢀH, d, J 2, 2H), 3.99 (CDꢀH, s, 5H), 5.08
[CH3C(CH)2, d, J 6, 2H], 5.22 [(CH3)2CHC(CH)2, d, J
6, 2H], 7.32–7.71 (Ph, m, 10H). 13C{1H} NMR: l 17.30
(CH3, s), 21.48 [CH(CH3)2, s], 25.36 (FcCH2P, d, J 22),
30.00 [CH(CH3)2, s], 67.04 (CA, s), 68.75 (CD, s), 70.05
(CB, s), 80.72 (CC, d, J 9), 85.61 [CH3C(CH)2, d,
of petroleum spirits (b.p. 40–60°C) into
a
dichloromethane solution at 4°C gave 4 as a brown
powder (0.086 g, 83%). M.p. 203–205°C (decomp.) lit.:
207–209°C [7]. Found: C, 68.4; H, 5.1%. C23H21FeOP
requires: C, 69.0; H, 5.3%. IR (cm−1): 1437(m),
1385(w), 1208(w), 1183(s), 1121(m), 1101(m), 1071(w),
1001(w), 928(w), 821(m), 744(s), 726(s), 696(s), 604(w),
537(s), 508(m), 490(s). ESMS (positive-ion, cone voltage
J
5], 90.08 [(CH3)2CHC(CH)2, d,
J
4], 94.09
[CH3C(CH)2, s], 108.40 [(CH3)2CHC(CH)2, s], 127.79–
133.95 (Ph, m).
Goodwin, Nicholas J.
