Reactivity of [(C
2
F
5
)
2
MeP]
2
Pt(Me)X
Organometallics, Vol. 23, No. 3, 2004 407
Alter n a tive Syn th esis of (d fep e)P tMe
reported synthesis of (dfepe)PtMe requires (dfepe)PtCl
time-consuming starting material to prepare. A more practi-
cal synthesis uses (cod)PtMe as a precursor: To 0.80 g of (cod)-
PtMe dissolved in 60 mL of ether was added 0.75 mL of dfepe
1.5 g, 1.2 equiv) via syringe. After stirring overnight the
2
. The originally
Hz). 13C NMR (100.6 MHz, CF
3
CO
2
D, 27 °C): δ 0.7 (q, 1J CH
)).
)
1
2
2
, a
136 Hz; P(CH
3
)), -31.7 (q, J CH ) 1357 Hz; Pt(CH
3
4
h
tr a n s-(d fm p ) P t(Me)(OTf) (6). A mixture of 217 mg (0.274
2
2
mmol) of cis-(dfmp) Pt(Me) in ca. 3 mL of HOTf was stirred
2
2
2
for 10 min, and all volatiles were removed by vacuum. The
solid residue was dissolved in 7 mL of diethyl ether and then
precipitated at -78 °C and cold filtered to give 185 mg of a
white solid (73%). NOTE: since complex 6 decomposes in ether
at ambient temperatures, the precipitation step must be
carried out quickly. Although NMR indicate isolated 6 to be
essentially pure, elemental analysis was low in carbon. Anal.
(
volatiles were removed and the residue was extracted with
petroleum ether. Concentration of the filtrate and cooling to
-
78 °C afforded 1.61 g (85%) of white crystalline (dfepe)PtMe
cis-[(C P P h ](Me S)P tMe (1). A 5 mm NMR tube was
charged with 10 mg of [Me Pt(µ-SMe )] (0.017 mmol), 94 µL
of (C PPh (0.51 mmol), and 0.5 mL of benzene-d . NMR
spectra indicated the exclusive formation of cis-[(C PPh]-
Me S)PtMe , with no spectroscopic changes after warming for
2
.
2
F
5
)
2
2
2
2
2
2
Calcd for C12
9 23 3 2
H F O P PtS: C, 15.54; H, 0.98. Found: C, 14.69;
2
F
5
)
2
6
-
1
H, 1.18. IR (Nujol, cm ): 1332 (s), 1301 (vs), 1226 (vs), 1142
2
5 2
F )
1
(
s), 992 (s), 974 (s). H NMR (400 MHz, C
6
D
6
, 27 °C): δ 1.87
)), 0.95 (s, br, ( J PtH ) 82 Hz, 3H; Pt(CH )).
P NMR (161.7 MHz, C D , 27 °C): δ 36.9 (m, J ) 3860
(
2
2
2
(
s, br, 6H; P(CH
3
3
several hours at 90 °C. No attempt was made to isolate this
3
1
1
1
product. H NMR (400 MHz, 27 °C): δ 8.05 (m, 2H; P(C
6
H
5
)),
6
6
PtP
Hz). 1H NMR (400 MHz, HOTf, 27 °C): δ 1.31 (s, br, 6H;
3
6
(
9
2
.96 (m, 3H; P(C
d, J PH ) 8 Hz, J PtH ) 73 Hz, 3H; Pt(CH
6
2
H
5
)), 1.79 (s, J PtH ) 26 Hz, 6H; S(Me)
2
3
), 1.21
)), 1.05 (d, J PH
2
3
3
P(CH )), 0.48 (t, ( J
) 82 Hz, J
) 13 Hz, 3H; Pt(CH )).
)
3
PtH
PH
3
3
3
1
1
Hz, 2
31
P NMR (161.7 MHz, HOTf, 27 °C): δ 38.2 (m, J
) 3795
J
PtH ) 83 Hz, 3H; Pt(CH
3
)). P NMR (161.9 MHz,
PtP
Hz). 13C NMR (100.6 MHz, HOTf, 27 °C): δ 1.3 (q, J ) 137
1
1
7 °C): δ 43.8 (m, J PtP ) 1705 Hz).
cis-(d fm p ) P t(Me) (2). A 25 mL flask was charged with
00 mg (1.58 mmol) of (nbd)PtMe and 750 µL of dfmp (3.94
CH
1
Hz; P(CH
tr a n s-(d fm p )
0.266 mmol) of cis-(dfmp)
3
)), -23.8 (q, J CH ) 142 Hz; Pt(CH
3
)).
F ) (7). A mixture of 211 mg
Pt(Me) in ca. 3 mL of FSO H was
2
2
2
P t(Me)(OSO
2
5
2
(
2
2
3
mmol) and placed on a filtration assembly. To this mixture
was added 10 mL of petroleum ether at -78 °C, and the
solution was warmed to ambient temperature with stirring.
After 45 min the volatiles were removed under vacuum and
the residue was redissolved in 10 mL of petroleum ether and
cooled to -78 °C. The resulting white microcrystalline solid
was isolated by cold filtration and dried under vacuum,
yielding 0.98 g (79%) of 2 (mp 34-35 °C). Anal. Calcd for
stirred for 10 min, and all volatiles were removed by vacuum.
The resulting oil was dissolved in 7 mL of diethyl ether and
then precipitated at -78 °C and cold filtered to give 127 mg
of a white solid that was contaminated by 0.7 equiv of
fluorosulfonic acid. Reprecipitation from ether yielded acid-
free product. NOTE: as with complex 7, the precipitation from
ether must be carried out quickly to avoid decomposition in
this solvent. Anal. Calcd for C11
H
9
F
21
O
3
P
2
PtS: C, 15.06; H,
1.03. Found: C, 14.78; H, 1.21. H NMR (400 MHz, C , 27
)), 0.92 (br s, J PtH )
C
12
H
12
F
20
P
2
Pt: C, 18,17; H, 1.53. Found: C, 18.46; H, 1.43.
H NMR (400 MHz, C , 27 °C): δ 1.53 (m, 6H; P(CH )), 1.26
)). P NMR (161.7
, 27 °C): δ 32.9 (m, J PtP ) 1500 Hz).
P t (3). A mixture of (cod)Pt(Ph) (200 mg, 0.437
1
1
6 6
D
6
D
6
3
3
2
3
2
31
°C): δ 1.78 (s, J PtH ) 28 Hz, 6H; P(CH
3
(t, J PH ) 8.7 Hz, J PtH ) 76 Hz, 6H; Pt(CH
3
82 Hz, 3H; Pt(CH
3
)). 31P NMR (161.7 MHz, C
6
D
6
, 27 °C): δ
1
MHz, C
6 6
D
1
1
3
6.5 (m, J PtP ) 3870 Hz). H NMR (400 MHz, FSO
3
2
H, 27 °C):
)), 0.46 (t, ( J PtH ) 87
(
d fm p )
4
2
3
δ 1.29 (br s, J PtH ) 35 Hz, 6H; P(CH
Hz, J PH ) 14 Hz, 3H; Pt(CH
2
3
mmol) and dfmp (415 µL, 2.19 mmol) was combined in a 25
mL RB flask. After cooling the reactants to -78 °C, 10 mL of
diethyl ether was added. Warming the mixture to ambient
temperature and stirring 24 h produced a yellow homogeneous
solution. Removal of volatiles and addition of ca. 5 mL of
methanol produced a light yellow solid, which was collected
by filtration and dried under vacuum (0.147 g, 25%). NMR of
the filtrate residue indicated the presence of unreacted (cod)-
3
31
3
)). P NMR (161.7 MHz, FSO
3
H,
1
13
7 °C): δ 38.2 (m, J PtP ) 3760 Hz). C NMR (100.6 MHz,
1
FSO
3
1
H, 27 °C): δ 116.9 (qm, J CF ) 288 Hz; CF
2
CF
3
), 114.5
)),
), 0.4 (q, 1J CH ) 138 Hz; P(CH
(
-
tm, J CF ) 294 Hz; CF
2
CF
3
3
22.6 (q, 1J CH ) 140 Hz; Pt(CH
3
)).
(8). A flask was charged with
.208 g (0.262 mmol) of 2, and ca. 3 mL of trifluoroacetic acid
[
2 3 2
(d fm p )P t(Me)(µ-O CCF )]
0
was condensed in at -78 °C. Upon warming to ambient
temperature, the evolution of methane was noted and the
reaction mixture was stirred for 20 min. The solution volume
was reduced to ∼1 mL, and 10 mL of methanol was added in
an effort to precipitate initially formed 5. No precipitation was
observed down to -78 °C, so the volatiles were removed and
the resulting white solid was suspended in ∼5 mL of petroleum
ether, cooled to -78 °C, and isolated by filtration. The obtained
product (52.5 mg, 33%) was identified by NMR as not 5, but
PtMe
2
. Anal. Calcd for C20
H
12
F
40
P
4
Pt: C, 18.61; H, 0.67.
, 27 °C): δ
)). P NMR (161.7 MHz, C
1
Found: C, 18.34; H, 1.17. H NMR (400 MHz, C
6
D
6
2
31
1
2
.53 (s, J PH ) 34 Hz; P(CH
7 °C): δ 59.8 (m, J PtP ) 4805 Hz).
3
6 6
D ,
1
2
cis-(d fm p )(CO)P t(Me) (4). One atmosphere of CO was
admitted to a stirred solution of 210 mg of 2 in 5 mL of
petroleum ether at ambient temperature. After 20 min,
complete displacement of dfmp by CO was confirmed by NMR.
Removal of volatiles gave 4 as a volatile colorless oil. IR
compound 7. Anal. Calcd for C16
Found: C, 16.00; H, 0.94. IR (Nujol, cm ): 1667(s), 1629(vw),
418(vw), 1307(s), 1224(vs), 1199(w), 1148(vs), 1120(w), 974-
12 26 2 2
H F P Pt : C, 15.82; H, 1.00.
-
1
(
(
chloroform, cm ): 2101 (vs), 1295 (s), 1218 (s), 1140 (m), 970
-1
1
2
m). H NMR (400 MHz, C
6
D
6
, 27 °C): δ 1.41 (d, J PtH ) 81
1
3
3
2
Hz, J PH ) 8 Hz, 3H; Pt(CH
3
2
)), 1.21 (d, J PtH ) 18 Hz, J PH
)
1
(m), 904(m), 883(m), 860(w), 749(m), 731(m). H NMR (400
3
8
Hz, 3H; P(CH
3
)), 0.81 (d, J PtH ) 71 Hz, J PH ) 12 Hz, 3H;
3
2
MHz, CDCl , 27 °C): δ 1.93 (d, J PtH ) 52 Hz, J PH ) 11 Hz,
3
3
1
Pt(CH
3
)). P NMR (161.7 MHz, C
6
D
6
, 27 °C): δ 37.9 (m,
2
)). 31P NMR
3
6
H; P(CH
3
)), 1.03 (s, J PtH ) 70 Hz, 6H; Pt(CH2
1
J
PtP ) 1310 Hz).
tr a n s-(dfm p) P t(Me)(O
Pt(Me) with either a stoichiometric amount of trifluoroacetic
acid in CDCl or dissolution in neat trifluoroacetic acid cleanly
produces trans-(dfmp) Pt(Me)(O CCF ) in solution. All at-
tempts to isolate 5 resulted in dfmp loss and dimerization to
form [(dfmp)Pt(Me)(µ-O CCF )] . Spectroscopic data for 5 in
H NMR (400 MHz, 27 °C): δ 1.99 (s, br, J PtH ) 30
(
161.7 MHz, CDCl
3
, 27 °C): δ 24.3 (ps pentet, J PF ) 69 Hz,
PtP ) 6005 Hz). C NMR (100.6 MHz, C D , 27 °C): δ 2.6
6 6
(dq, J CH ) 136 Hz, J PC ) 34 Hz; P(CH )), -19.7 (q, J CH
136 Hz; Pt(CH )).
Cr ysta l Str u ctu r e of cis-(d fm p ) P t(Me) (2). Colorless
2 2
1
13
2
2
CCF
3
) (5). Treatment of cis-(dfmp)-
J
1
1
1
2
3
)
3
3
2
2
3
prismatic crystals suitable for X-ray analysis deposited from
an oily sample of impure 2 upon standing for several days at
ambient temperature. A crystal of suitable size was affixed
onto a glass fiber with epoxy. Data were collected using a
Siemens P4 diffractometer using monochromatic molybdenum
radiation and an LT-2 nitrogen stream low-temperature
apparatus operating at 173 K. A summary of crystal data is
presented in Table 1. A monoclinic cell was determined based
2
3
2
1
3
CDCl
Hz, 6H; P(CH
(
3
:
2
3
3
)), 0.87 (t, J PtH ) 78 Hz, J PH ) 6 Hz, 3H; Pt-
1
3
1
CH
3
)). P NMR (161.7 MHz, 27 °C): δ 33.1 (m, J PtP ) 3840
1
Hz). Spectroscopic data for 5 in CF
3
CO
2
H: H NMR (400 MHz,
2
2
7 °C): δ 1.99 (s, br, 6H; P(CH
Pt(CH )). P NMR (161.7 MHz, 27 °C): δ 26.3 (m, J PtP ) 3840
3
)), 0.93 (t, J PtH ) 80 Hz, 3H;
3
1
1
3
Butikofer, Jeffrey L.
