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T.V.V. Ramakrishna, A.J. Elias / Journal of Organometallic Chemistry 637–639 (2001) 382–389
3.4.3. FcCH2P(S)(CH2O)2PN2P[N(Me)CH2]2[NS(O)Ph]
(10)
3.4.5. FcCH2P(S)[(CH2O)2PN2P(OCH2CF2)2]-
[NS(O)4-ClꢀC6H4] (12)
n-Butyllithium (1.93 ml, 3.00 mmol), FcCH2-
P(S)(CH2OH)2 (6) (0.50 g, 1.54 mmol) in THF (15 ml)
and (NPCl2)NP[N(Me)CH2]2[NS(O)Ph] (4) (0.60 g, 1.55
mmol) in THF (5 ml) were reacted and worked up as
described for 8. The solid obtained was purified over a
silica gel column using a mixture of hexane and EtOAc
(7.7:2.3) as eluent. Recrystallization from CH2Cl2–hex-
ane mixture (3:7) gave orange–red crystals, which were
identified as FcCH2P(S)(CH2O)2PN2P[N(Me)CH2]2-
A solution of (CF2CH2OH)2, (0.50 g, 3.08 mmol) in
THF (15 ml), n-butyllithium (3.86 ml, 6.17 mmol) and
(NPCl2)2[NS(O)4-ClꢀC6H4] (3) (1.30 g, 3.09 mmol) in
THF (10 ml) were reacted as described for 8. This
reaction mixture was slowly added using a cannula to
the solution of FcCH2P(S)(CH2OH)2 (6) (1.00 g, 3.08
mmol) in THF (15 ml) and reacted with n-butyllithium
(3.86 ml, 6.17 mmol) according to procedure described
for 8 at −80 °C. The reaction mixture was slowly
brought to r.t. and stirred for 10 h. The solvent was
removed at reduced pressure and the crude sample
obtained was purified over silica gel using EtOAc and
hexane (1.6:8.5) as eluent to obtain an orange solid
which was later identified as FcCH2P(S)[(CH2-
O)2PN2P(OCH2CF2)2][NS(O)4-ClꢀC6H4] (12) (1.50 g,
65%); m.p.: 170 °C. IR (cm−1, Nujol): 1290m, 1275m,
1250m, 1235s, 1195vs, 1165w, 1140s, 1080s, 1040vs,
1000w, 900m, 870w, 810m, 795w, 740s, 710w, 660w.
1H-NMR (CDCl3): l 3.35 (m, FcꢀCH2, 2H), 4.93–4.08
(m, CAH, CBH, CDH, OCH2CF2 and PCH2O, 17H),
7.40 (d, CGH, 2H), 7.72 (d, CFH, 2H). 13C{1H}-NMR
(CDCl3): l 29.52 (FcꢀCH2), 62.01 (OCH2CF2), 66.76
(PꢀCH2ꢀO), 68.89 (CA), 69.09 (CD), 69.51 (CB), 75.10
(CC), 112.32 (CF2), 126.69 (CGH), 129.26 (CFH),
[NS(O)Ph] (10) (0.66g, 70%); m.p.: 210 °C. IR (cm−1
,
Nujol): 1295w, 1240s, 1220s, 1200vs, 1190s, 1160s,
1095w, 1040vs, 930w, 895w, 875s, 800s, 720m, 700w,
680w, 630w. 1H-NMR (CDCl3): l 2.19 (d, NꢀCH3,
3H), 2.51 (d, NꢀCH3, 3H), 3.13 (m, NꢀCH2, 4H), 3.40
(m, FcꢀCH2, 2H), 4.12–4.84 (m, CAH, CBH, CDH, and
PCH2O, 13H), 7.37 (m, CGH, CHH, 3H), 7.87 (m, CFH,
2H). 13C{1H}-NMR (CDCl3): l 29.35 (FcꢀCH2), 30.85
(NꢀCH3), 47.16 (NꢀCH2ꢀCH2ꢀN), 65.96 (PꢀCH2ꢀO),
68.68 (CA), 69.02 (CD), 69.57 (CB), 75.51 (CC), 125.13
(CG), 128.64 (CF), 131.51 (CH). 31P{1H}-NMR (CDCl3):
l
14.90 (dd, 2Jp–p=61.45 Hz, 3Jp–p=16.17 Hz,
2
CH2ꢀOꢀP), 21.38 [d, Jp-p=61.45 Hz, PꢀN(CH3)CH2],
23.09 [d, 3Jp–p=16.17 Hz, FcꢀCH2ꢀP(S)]. FABMS;
m/e (fragment, relative intensity): 637 ([M+], 100), 199
([FcCH+2 ], 90), 212 ([P2N3S−Ph], 2), 136 ([P2N3S], 20).
3
138.73(CH). 31P{1H}-NMR (CDCl3): l 10.76 (dd, JP–
P=14.60 Hz, 2JP–P=84.08 Hz, CH2OP), 11.90 (d,
3
3.4.4. FcCH2P(S)(CH2O)2PN2P(N(Me)CH2)2]-
2JP–P=84.08 Hz, POCH2), 21.99 (d, JP–P=14.60 Hz,
[NS(O)4-ClꢀC6H4] (11)
FcCH2P) (isomer I); 9.63 (dd, 3JP–P=17.78 Hz,
2JP–P=103.49 Hz, CH2OP), 13.89 (d, 2JP–P=103.49
Hz, POCH2), 19.79 (d, 3JP–P=17.78 Hz, FcCH2P)
(isomer II). FABMS; m/e (fragment, relative intensity):
745 ([M+], 50), 744 ([M+−1], 100), 199 ([FcCH+2 ],
100). Anal. Found: C, 37.11; H, 3.16; N, 5.59. Calc. for
C23H23ClF4FeN3O5P3S2: C, 37.04; H, 3.11; N, 5.63%.
n-Butyllithium (1.93 ml, 3.00 mmol), FcCH2P-
(S)(CH2OH)2 (6) (0.50 g, 1.54 mmol) in THF (15 ml)
and (NPCl2)NP[N(Me)CH2]2[NS(O)4-ClꢀC6H4] (5)
(0.65 g, 1.55 mmol) in THF (10 ml) were reacted and
worked up as described for 8. The solid obtained was
purified over a silica gel column using a mixture of
EtOAc and hexane (3:7) as eluent. The orange product
obtained was characterized as FcCH2P(S)(CH2O)2-
PN2P[N(Me)CH2]2[NS(O)4-ClꢀC6H4] (11) (0.64g, 65%);
m.p.: 190 °C. IR (cm−1, Nujol): 1249s, 1230w, 1210vs,
1190w, 1169m, 1105m, 1037s, 950w, 890s, 820s, 730s,
3.4.6. {[CH2N(Me)]2PN2P(OCH2CF2)2}[NS(O)Ph] (13)
n-Butyllithium (3.86 ml, 6.17 mmol), (CF2CH2OH)2,
(0.50 g, 3.08 mmol) in THF (15 ml) and
(NPCl2)NP[N(Me)CH2]2[NS(O)Ph], (4) (1.19 g, 3.08
mmol) in THF (5 ml) were reacted and worked up as
described for 8. The residue obtained showed two close
spots in TLC analysis and were separated over a silica
gel column using a mixture of EtOAc and hexane (3:7)
as eluent. The product obtained was a viscous liquid
which was characterized as {[CH2N(Me)]2PN2-
P(OCH2CF2)2}[NS(O)Ph] (131) (1.02 g, 73% overall
yield). IR (cm−1, neat): 1233vs, 1139w, 1076vs, 925w,
1
707w, 638m. H-NMR (CDCl3): l 2.21(d, NꢀCH3, 3H),
2.53 (d, NꢀCH3, 3H), 3.13 (m, NꢀCH2, 4H), 3.4 (m,
FcꢀCH2, 2H), 4.83–4.05 (m, CAH, CBH, CDH, and
PCH2O, 13H), 7.35 (d, CGH, 2H), 7.79 (d, CFH, 2H).
13C{1H}-NMR (CDCl3): l 29.38 (FcꢀCH2), 30.84
(NꢀCH3), 47.06 (NꢀCH2ꢀCH2N), 66.00 (PꢀCH2ꢀO),
68.78 (CA), 69.06 (CD), 69.57 (CB), 75.48 (CC), 126.70
(CG), 128.87 (CF), 137.74 (CH). 31P{1H}-NMR (CDCl3):
1
l
14.78 (dd, 2Jp–p=63.06 Hz, 3Jp–p=14.60 Hz,
809s, 752s, 670w, 625s. H-NMR (CDCl3): l 2.23 (d,
CH2ꢀOꢀP), 21.29 [d, 2Jp–p=63.06 Hz, PꢀN(CH3)CH2],
22.76 [d, 3Jp–p=14.60 Hz, FcꢀCH2ꢀP(S)]. FABMS;
m/e (fragment, relative intensity): 671 ([M+], 80), 199
([FcCH+2 ], 100), 212 ([P2N3S−Ph], 2), 136 ([P2N3S],
60). Anal. Found: C, 41.08; H, 4.40; N, 10.38. Calc. for
C23H29ClFeN5O3P3S2: C, 41.12; H, 4.35; N, 10.42%.
NꢀCH3, 2H), 2.52 (d, NꢀCH3, 2H), 3.13 (m, NꢀCH2,
4H), 4.36 (m, OꢀCH2, 4H), 7.34 (d, CGH, 2H), 7.77 (d,
CFH, 2H). 13C{1H}-NMR (CDCl3): l 30.89 (NꢀCH3),
1 The 1H- and 13C-NMR shifts of these isomers showed very little
difference.