I. Ara et al. / Inorganica Chimica Acta 358 (2005) 315–324
317
1058 (s), 958 (vs), 836 (w, X-sensitive [18]), 674 (s), 625
(m); m(Sn–Cl) 335 (vs), 325 (vs); PPh3 1104 (s), 746 (s),
693 (s), 534 (vs), 511 (s), 493 (s); NBu4 887 (m, br).
0.018 g (0.068 mmol) of PPh3 was added. The mixture
was reacted at room temperature for 2 h and evapo-
rated to dryness. The residue was treated with isopro-
pyl alcohol to render a white solid, (NBu4)[trans-
Pt(SnCl3)(C6F5)2PPh3] (8), which was filtered, washed
with isopropyl alcohol and n-hexane and air dried.
Yield: 71%. Anal. Calc. for C46H51Cl3F10NPPtSn: C,
43.88; H, 4.08; N, 1.11. Found: C, 44.16; H, 4.12;
N, 1.08%. Molar conductivity: 113 S cm2 molꢀ1. IR
(cmꢀ1): C6F5 1632 (w), 1603 (w), 1057 (s), 957 (vs),
777 (m, X-sensitive [18]); m(Sn–Cl) 325 (s); PPh3
1099 (s), 736 (s), 698 (s), 527 (s), 515 (s), 498 (m);
NBu4 890 (m). NMR (20 ꢁC, CDCl3) 19F d ꢀ115.5
1
NMR (20 ꢁC): 31P (CDCl3) d 11.4 (s, JPt–P = 1004 Hz,
2
2JSn–P = 91Hz, JSn–P = 95 Hz); 119Sn (CD2Cl2) d 15.1
(d, 1JPt–Sn = 27050 Hz, 2JP–Sn = 225 Hz). MS
FAB(ꢀ):m/z 1157 molecular peak (38%), 967 [Pt(SnCl3)
Cl(C6Cl5) PPh3] (64%), 705 [Pt(SnCl3)Cl(C6Cl5)] (25%).
2.2.6. Preparation of (NBu4)2[trans-Pt2(l-Cl)2(C6F5)2
(SnCl3)2] (6)
0.15 g (0.10 mmol) of (NBu4)2[trans-Pt(C6F5)2-
(SnCl3)2] was reacted with PtCl2 (0.027 g, 0.10 mmol) in
15 mL of refluxing acetone for 10 h, the initial suspension
giving rise to a brown-green solution. The mixture was fil-
tered off in order to eliminate the small quantity of solids
in suspension and the filtrate was evaporated to dryness.
Upon addition of diethyl ether to the oily residue, a
light brown solid was obtained, which was filtered
off and air dried. Yield: 86%. Anal. Calc. for
C44H72Cl8F10N2Pt2Sn2: C, 30.51; H, 4.16; N, 1.62.
Found: C, 30.63; H, 4.30; N, 1.64%. Molar conductivity:
217 S cm2 molꢀ1. IR (cmꢀ1): C6F5 1638 (w), 1608 (w),
1057 (vs), 961 (vs), 809 (s, X-sensitive [18]); m(Sn–Cl)
354 (s), 338 (vs); NBu4 876 (m). NMR (20C, CDCl3)
3
(d, 4Fo, JPt–Fo = 242 Hz), ꢀ163.9 (t, 2Fp), ꢀ164.7
1
to ꢀ164.9 (multiplet, 4 Fm). 31P d 14.7 (s, JPt–
P = 1178 Hz). MS FAB(ꢀ):m/z 1021 molecular peak
(20%), 412 [Pt(SnCl3)] (38%).
2.2.9. Reaction of (NBu4)2[trans-Pt(SnCl3)2(C6F5)2]
with L (L = PPh3, PEtPh2, PEt2Ph, PEt3) (1:2)
L = PPh3. (NBu4)2[trans-Pt(SnCl3)2(C6F5)2] (0.100 g,
0.068 mmol) was dissolved in 20 mL of acetone along
with 0.036 g (0.14 mmol) of PPh3. The mixture was re-
acted for 15 h at room temperature and evaporated to
dryness. A few milliliters of isopropyl alcohol was added
to the residue and, after a vigorous stirring, a white solid
was formed, [trans-Pt(C6F5)2(PPh3)2], which was fil-
tered, washed with n-hexane and air dried. Yield: 72%.
Anal. Calc. for C48H30F10P2Pt: C, 52.71; H, 2.87.
Found: C, 52.35; H, 2.82%.
3
19F dꢀ118.4 (dd, 2Fo, JPt–Fo = 341 Hz), ꢀ160.7 (td,
1Fp), ꢀ164.1 to ꢀ165.0 (multiplet, 2Fm). MS FAB(ꢀ):
molecular
[Pt(SnCl3)2Cl(C6F5)] (15%), 565 [Pt(C6F5)2Cl] (100%).
peak
not
observed,
m/z
623
L = PEtPh2. 0.100 g (0.068 mmol) of (NBu4)2[trans-
Pt(SnCl3)2(C6F5)2] and 42 lL (0.21 mmol) of PEtPh2
gave 0.047 g of [trans-Pt(C6F5)2(PEtPh2)2] (72% yield).
Anal. Calc. for C40H30F10P2Pt: C, 50.17; H, 3.16.
Found: C, 49.74; H, 3.07%.
L = PEt2Ph. 0.100 g (0.068 mmol) of (NBu4)2[trans-
Pt(SnCl3)2(C6F5)2] and 36 lL (0.21 mmol) of PEt2Ph
gave 0.040 g of [trans-Pt(C6F5)2(PEt2Ph)2] (68% yield).
Anal. Calc. for C32H30F10P2Pt: C, 44.61; H, 3.91.
Found: C, 44.64; H, 4.01%.
L = PEt3. 0.100 g (0.068 mmol) of (NBu4)2[trans-
Pt(SnCl3)2(C6F5)2] and 30.3 lL (0.246 mmol) of PEt3in
30 mL of acetone were refluxed for 30 h. After evaporat-
ing to dryness, the residue was treated with diethyl ether
to give 0.034 g of [trans-Pt(C6F5)2(PEt3)2] (65% yield),
which was filtered and air dried. Anal. Calc. for
C32H30F10P2Pt: C, 35.66; H, 3.55. Found: C, 35.20; H,
3.58%.
2.2.7. Preparation of (NBu4)2[trans-Pt2(l-Cl)2(C6Cl5)2
(SnCl3)2] (7)
(a) Under the same conditions described above
(NBu4)2[trans-Pt(C6Cl5)2(SnCl3)2] (0.15 g, 0.092 mmol)
was reacted with PtCl2 (0.024 g, 0.097 mmol) to render
a brown-yellow solid. Yield: 74%. Anal. Calc. for
C44H72Cl18N2Pt2Sn2: C, 27.86; H, 3.80; N, 1.48. Found:
C, 28.13; H, 3.69; N, 1.68%. Molar conductivity: 220
S cm2 molꢀ1. IR (cmꢀ1): C6Cl5 1322 (s), 1295 (s), 1262
(s), 1224 (m), 800 (w, X-sensitive [18]), 676 (s), 637
(m); m(Sn–Cl) 349 (s), 326 (vs); NBu4 882 (m, br). MS
FAB(ꢀ): molecular peak not observed, m/z 728
[PtCl(C6Cl5)2] (62%), 704 [Pt(SnCl3)Cl(C6Cl5)] (53%),
515 [PtCl2(C6Cl5)] (100%). (b) 0.15 g (0.099 mmol) of
(NBu4)2[trans-Pt(l-Cl)2Cl2(C6Cl5)2] was dissolved in 25
mL of acetone and SnCl2 (0.0375 g, 0.198 mmol) was
added. After reacting at room temperature for 2 h, the
suspension was filtered off and the filtrate evaporated
to dryness. The residue was treated with isopropyl alco-
hol to render a solid which was filtered, washed with iso-
propyl alcohol and air dried. Yield: 60%.
2.2.10. Reaction of (NBu4)2[trans-Pt2(l-Cl)2(SnCl3)2
(C6X5)2] with PPh3 (1:2)
X = F. (NBu4)2[trans-Pt2(l-Cl)2(SnCl3)2(C6F5)2] (0.100
g, 0.058 mmol) was dissolved in 30 mL of dichloro-
methane and reacted with 0.030 g (0.12 mmol) of
PPh3. The solution turned deep orange and after 3 h
of stirring at room temperature was evaporated to
2.2.8. Reaction of (NBu4)2[trans-Pt(SnCl3)2(C6F5)2]
with PPh3 (1:1)
0.100 g (0.068 mmol) of (NBu4)2[trans-Pt(SnCl3)2-
(C6F5)2] was dissolved in 20 mL of acetone and