4990 Organometallics, Vol. 27, No. 19, 2008
de Quadras et al.
trans,trans-(C6F5)(Et3P)2Pt(Ct C)2Pt(Pp-tol3)2(p-tol) (9). A
Schlenk flask was charged with 6 (0.162 g, 0.250 mmol), trans-
(p-tol)(p-tol3P)2PtCl (4;3 0.233 g, 0.250 mmol), t-BuOK (0.0338
g, 0.301 mmol), KPF6 (0.0561 g, 0.304 mmol), CuCl (0.0049 g,
0.049 mmol), THF (10 mL), and methanol (10 mL) with stirring.
After 96 h, the solvent was removed by oil pump vacuum. The
residue was extracted with CH2Cl2. The extract was filtered through
a short alumina/Celite pad. The solvent was removed by rotary
evaporation and oil pump vacuum to give 9 as a pale yellow solid
(0.350 g, 0.228 mmol; 91%), dec pt > 167 °C (gradual darkening,
then melting). Anal. Calcd for C71H79F5P4Pt2: C, 55.32; H, 5.17.
Found: C, 55.33; H, 5.17. DSC:38 endotherm with Ti, 105.3 °C;
Te, 108.9 °C; Tc, 122.0 °C; Tf, 122.2 °C; exotherm with Ti 122.2
°C; Te, 122.2 °C; Tc, 132.0 °C; Tf, 132.1 °C; endotherm with Ti,
132.2 °C; Te, 132.2 °C; Tc, 143.5 °C; Tf, 144.5 °C; endotherm with
Ti, 163.8 °C; Te, 179.6 °C; Tc, 187.6 °C; Tf, 191.2 °C. TGA: weight
loss 36%, 195-403 °C. NMR (δ, CDCl3): 1H 7.43-7.39 (m, 12H,
177.8 °C. TGA: weight loss 26%, 236-410 °C. NMR (δ, CDCl3):
1H 7.50-7.47 (m, 12H, o to P), 7.28-7.24 (m, 12H, o to P′), 7.06
3
3
(d, 12H, JHH ) 7.2 Hz, m to P), 6.95 (d, 12H, JHH ) 7.2 Hz, m
3
3
to P′), 6.27 (d, JHH ) 2H, 7.3 Hz, o to Pt), 6.02 (d, JHH ) 7.1
Hz, 2H, m to Pt), 2.32 (s, 18H, CH3 p to P), 2.22 (s, 18H, CH3 p
to P′), 1.93 (s, 3H, CH3 p to Pt); 13C{1H}40 150.3 (t, JCP ) 9.9
2
1
Hz, i to Pt), 145.7 (dm, JCF ) 254.0 Hz, o-C6F5), 140.8 (s, p to
P), 140.3 (s, p to P′), 139.1 (s, o to Pt), 134.6 (virtual t, 2JCP ) 6.1
Hz,41 o to P), 134.4 (virtual t, JCP ) 6.3 Hz,41 o to P′), 129.0 (s,
2
p to Pt), 128.4 (virtual t, JCP ) 5.3 Hz,41 m to P), 128.2 (virtual
3
t, 3JCP ) 5.3 Hz,41 m to P′), 127.7 (virtual t, 1JCP ) 29.9 Hz,41 i to
2
P; i to P′ obscured), 127.5 (s, m to Pt), 109.9 (t, JCP ) 15.2 Hz,
p-tolPtCt ), 99.2 (s, PtCt C), 98.4 (s, PtC≡C), 93.5 (br s,
C6F5PtCt ), 61.3 (s, PtCt CC), 60.2 (s, PtCt CC), 21.29 (s, CH3 p
to P), 21.27 (s, CH3 p to P′), 20.5 (s, CH3 p to Pt); 31P{1H} 18.7
(s, 1JPPt ) 2955 Hz, Pp-tol),39 17.2 (s, 1JPPt ) 2689 Hz, PC6F5).39 IR
(cm-1, powder film): νCt 2104 (m). UV-vis (CH2Cl2, 1.25 ×
C
o to P), 6.98 (d, 12H, 3JHH ) 7.7 Hz, m to P), 6.29 (d, 2H, 3JHH
)
10-5 M):42 329 (32 100), 348 (14 800), 376 (8400). MS:43 1937
(M+, 10%), 970 ([(C6F5)(tol3P)2Pt]+, 20%), 894 ([(tol)(tol3P)2Pt]+,
30%), 803 ([(tol3P)2Pt]+, 100%).
3
7.7 Hz, o to Pt), 5.98 (d, 2H, JHH ) 7.5 Hz, m to Pt), 2.29 (s,
18H, CH3 p to P), 1.90 (s, 3H, CH3 p to Pt), 1.54-1.51 (m, 12H,
PCH2), 0.95-0.89 (m, 18H, PCH2CH3); 13C{1H}40 152.2 (s, i to
Pt), 139.2 (s, o to Pt), 139.1 (s, p to P), 134.6 (s, o to P), 128.9
(virtual t, 1JCP ) 29.0 Hz,41 i to P), 128.6 (s, p to Pt), 128.0 (s, m
to P), 127.4 (s, m to Pt), 103.1 (s, PtCt ), 99.4 (s, PtCt C), 96.0 (s,
PtCt C), 21.4 (s, CH3 p to P), 20.5 (s, CH3 p to Pt), 15.5 (virtual
trans,trans-(C6F5)(Et3P)2Pt(Ct C)3Pt(PEt3)2(p-tol) (17). A round-
bottom flask was charged with 7 (0.113 g, 0.203 mmol), KPF6
(0.041 g, 0.22 mmol), t-BuOK (0.0270 g, 0.243 mmol), CuCl
(0.0040 g, 0.0040 mmol), THF (10 mL), and methanol (10 mL). A
Schlenk flask was charged with trans-(C6F5)(Et3P)2Pt(Ct C)3SiEt3
(15;7 0.154 g, 0.203 mmol) and CH2Cl2 (4 mL), and n-Bu4N+F-
(0.023 mL, 1.0 M in THF, 5 wt % H2O) was added with stirring.
After 15 min, the solution derived from 7 was transferred via syringe
to that derived from 15. The mixture was stirred overnight. The
precipitate was isolated by filtration, washed with ethanol, and dried
by oil pump vacuum to give 17 as a yellow solid (0.142 g, 0.120
mmol; 59%), dec pt > 211 °C (gradual darkening without melting).
Anal. Calcd for C43H67F5P4Pt2: C, 43.29; H, 5.66. Found: C, 42.26;
H, 5.66. DSC: no features below 200 °C. TGA: weight loss 47%,
235-410 °C. NMR (δ, CDCl3): 1H 7.11 (d, 2H, 3JHH ) 7.5 Hz, o
to Pt), 6.78 (d, 2H, 3JHH ) 7.5 Hz, m to Pt), 2.17 (s, 3H, CH3 p to
Pt), 1.78-1.67 (m, 24H, PCH2CH3 + P′CH2CH3), 1.10-1.02 (m,
36H, PCH2CH3 + P’CH2CH3); 13C{1H}40 150.3 (s, i to Pt), 138.9
(s, o to Pt), 130.6 (s, p to Pt), 128.6 (s, m to Pt), 109.2 (s, PtCt ),
93.3 (s, PtCt C), 93.1 (s, PtCt C), 60.8 (s, PtCt CC), 60.7 (s,
PtCt CC), 20.9 (s, CH3 p to Pt), 15.9 (virtual t, 1JPC ) 17.5 Hz,41
PCH2), 15.3 (virtual t, 2JPC ) 17.3 Hz,41 P′CH2), 8.1 (s, PCH2CH3),
1
t, JCP ) 17.5 Hz,41 PCH2), 7.8 (s, PCH2CH3); 31P{1H} 18.3 (s,
1
1JPPt ) 2987 Hz, Pp-tol3),39 12.9 (s, JPPt ) 2461 Hz, PEt3).39 IR
(cm-1, powder film), νCt C 2148 (w), 2001 (w); UV-vis (CH2Cl2,
1.25 × 10-5 M; MTHF, see Table 5 and Figure 5),42 300 (15 400),
324 (13800), 349 (13 300). MS:43 1541 (M+, 90%), 1449 ([M -
tol]+, 30%), 1358 ([M - C6F5]+, 3%), 950 ([M - C6F5 - PEt3 -
Ptol3]+, 100%).
trans,trans-(C6F5)(p-tol3P)2Pt(Ct C)3Pt(Pp-tol3)2(p-tol) (12).
A. A Schlenk flask was charged with 4 (0.0484 g, 0.0520 mmol),
HNEt2 (20 mL), and CuCl (0.0040 g, 0.040 mmol) with stirring
and cooled to -45 °C. Another Schlenk flask was charged with
trans-(C6F5)(p-tol3P)2Pt(Ct C)3SiEt3 (13,3 0.0600 g, 0.0520 mmol)
and CH2Cl2 (2 mL), and n-Bu4N+F- (0.016 mL, 1.0 M in THF, 5
wt % H2O) was added with stirring. After 15 min, the solution
derived from 13 was added via syringe to that of 4. The mixture
was allowed to warm at room temperature overnight. After 6 days,
the solvent was removed by oil pump vacuum. The residue was
extracted with hexanes (3 × 5 mL) and toluene (3 × 7 mL). The
extracts were passed in sequence through an alumina column (4 ×
1 cm), which was rinsed with toluene. The solvent was removed
from the toluene fractions by oil pump vacuum to give a mixture
of 12 and 13 (0.092 g) The solid was dissolved in CH2Cl2 and
layered with methanol. A yellow powder precipitated overnight,
which was collected by filtration and dried by oil pump vacuum to
give 12 as a yellow solid (0.0390 g, 0.0208 mmol; 40%).
B. A round-bottom flask was charged with 4 (0.0697 g, 0.0752
mmol), KPF6 (0.0152 g, 0.0825 mmol), t-BuOK (0.0092 g, 0.082
mmol), CuCl (0.0020 g, 0.0020 mmol), THF (10 mL), and methanol
(10 mL). A Schlenk flask was charged with 13 (0.087 g, 0.0751
mmol) and CH2Cl2 (4 mL), and n-Bu4N+F- (0.023 mL, 1.0 M in
THF, 5 wt % H2O) was added with stirring. After 15 min, the
solution derived from 4 was transferred via syringe to that derived
from 13. The mixture was stirred overnight. The precipitate was
isolated by filtration, washed with ethanol, and dried by oil pump
vacuum to give 12 as a yellow solid (0.0910 g, 0.0470 mmol; 63%),
dec pt > 221° (gradual darkening, then melting). Anal. Calcd for
1
8.0 (s, P′CH2CH3); 31P{1H} 13.1 (s, JPPt ) 2406 Hz, PC6F5),39
1
11.3 (s, JPPt ) 2620 Hz, Pp-tol).39 IR (cm-1, powder film): νCt
C
2150 (ms), 2096 (vw), 2003 (w). UV-vis (CH2Cl2, 1.25 × 10-5
M):42 281 (53 600), 299 (34 900), 312 (39 600), 342 (9500), 367
(5400). MS:43 1192 (M+, 100%), 597 ([(C6F5)(Et3P)2Pt]+, 20%),
522 ([(tol)(Et3P)2Pt]+, 60%).
trans-(C6F5)(Et3P)2Pt(Ct C)2Au(PPh3) (18). A Schlenk flask
was charged with 6 (0.100 g, 0.154 mmol), (Ph3P)AuCl (0.076 g,
0.154 mmol),21 and THF (5 mL) with stirring. Then KN(SiMe3)2
(0.610 mL, 0.5 M in toluene, 0.305 mmol) was added. After 18 h,
the volatiles were removed by oil pump vacuum. The residue was
extracted with CH2Cl2 (2 × 2 mL). The extract was filtered through
an alumina/Celite pad (2 × 1 cm). The solvent was removed by
rotary evaporation and oil pump vacuum to give 18 as a yellow
powder (0.166 g, 0.148 mol; 97%), dec pt > 190 °C (gradual
darkening, then melting). Anal. Calcd for C40H45AuF5P3Pt: C, 43.45;
H 4.10. Found: C, 43.76; H, 4.72. DSC:38 endotherm with Ti, 104.0
°C; Te, 107.6 °C; Tc, 120.6 °C; Tf, 123.3 °C; endotherm with Ti,
131.4 °C; Te, 137.0 °C; Tc, 148.4 °C; Tf, 155.5 °C; endotherm with
Ti, 185.2 °C; Te, 191.1 °C; Tc, 202.9 °C; Tf, 205.6 °C. TGA: weight
loss 38%, 206-404 °C. NMR (δ, CDCl3): 1H 7.48-7.37 (m, 15H,
Ph), 1.73-1.71 (m, 12H, PCH2), 1.04-0.96 (m, 18H, PCH2CH3);
C
103H91F5P4Pt2: C, 63.83; H, 4.73. Found: C, 63.03; H, 4.73. DSC:38
endotherm with Ti, 91.6 °C; Te, 110.8 °C; Tc, 132.3 °C; Tf, 138.1
°C; endotherm with Ti, 140.2 °C; Te, 158.2 °C; Tc, 174.8 °C; Tf,
13C{1H}40 146.8 (dm, 1JCF ) 197 Hz, o-C6F5), 136.5 (dm, 1JCF
)
(42) Absorptions are in nm (ε, M-1 cm-1).
(43) FAB, 3-NBA: m/z for the most intense peak of the isotope envelope;
relative intensities (%) are for the specified mass range.
197 Hz, m-C6F5), 134.2 (d, 2JCP ) 13.8 Hz, o to P), 131.4 (br s, p
to P), 129.8 (d, 1JCP ) 55.6 Hz, i to P), 129.0 (d, 3JCP ) 11.2 Hz,