D.A. Edwards et al. / Inorganica Chimica Acta 328 (2002) 134–146
137
133.6 (d, 8.3 Hz, PC6H5), 132.4 (d, J=11.9 Hz,
PC6H5), 129.7 (PC6H5), 128.5 (d, J=4.6 Hz, PC6H5).
31P NMR (20 °C, CDCl3): 8.01. 31P NMR (−80 °C,
CDCl3–CH2Cl2): 7.6 (dd, J=490 Hz). 109Ag NMR
(−80 °C, CDCl3/CH2Cl2): 907 (t, J=489 Hz).
2.2.14. O,O%-Perfluorobutyratobis(triphenyl-
phosphine)sil6er(I), Ag(O2CC3F7)(PPh3)2 (14)
Silver perfluorobutyrate (11) (0.4 g, 1.3 mmol) was
stirred in toluene (50 cm3 with an excess of
triphenylphosphine (2.0 g, 7.9 mmol). The mixture was
stirred in the absence of light for 24 h. The resulting
cream precipitate was filtered in air, washed with 2 cm3
of toluene and dried in vacuo. Yield 0.55 g, 52%. The
compound was recrystallised from a toluene–ethanol
2.2.11. O,O%-Pi6alatobis(triphenylphosphine)sil6er(I),
Ag(O2CC4H9 t)(PPh3)2 (11)
Yield 52%. Anal. Found (Calc. for C41H39O2AgP2) C,
solvent
mixture.
Anal.
Found
(Calc.
for
66.9 (67.1); H, 5.31(5.36)%. IR: 1225, 1406, 1435, 1477,
C40H30F7O2AgP2): C, 56.9 (56.8); 3.44 (3.58)%. M.p.
186 °C. IR: 1208, 1229, 1267, 1312, 1343, 1437, 1659.
13C NMR (CDCl3): 133.8 (d, J=18.4 Hz, PC6H5),
133.1 (d, J=18.3 Hz, PC6H5), 129.8 (PC6H5), 128.7 (d,
J=9.2 Hz, PC6H5). 19F NMR (CDCl3): −81.2 (t,
J=9.2 Hz, CF3), −117.3 (q, J=9.3 Hz, aCF2),
−127.3 (CF2). 31P NMR (20 °C, CDCl3): 5.7 (br). Ag
NMR (−80 °C, CDCl3/CH2Cl2): 823 (t, J=524 Hz).
Also prepared by the same method as that of 14
were.
1
1543. H NMR (CDCl3): 7.45–7.22 (m, 30H, C6H5),
1.23 (s, 9H, CCH3). 13C NMR (CDCl3): 185.2 (O2C),
133.9 (d, J=18.4 Hz, PC6H5), 132.5 (d, J=27.6 Hz,
PC6H5), 129.9 (PC6H5), 128.6 (d, J=9.2 Hz, PC6H5),
39.4 (CCH3), 28.7 (CCH3). 31P NMR (20 °C, CDCl3):
8.51. 31P NMR (−80 °C, CDCl3/CH2Cl2): 7.75 (dd,
J=480 Hz). Ag NMR (−80 °C, CDCl3/CH2Cl2): 931
(t, J=484 Hz).
2.2.12. O,O%-Mesitylatobis(triphenylphosphine)sil6er(I),
Ag(O2CC6H2Me3)(PPh3)2 (12)
2.2.15. O,O%-Perfluoroheptanoatobis(triphenyl-
phosphine)sil6er(I), Ag(O2CC6F13)(PPh3)2 (15)
Yield 6.5 mmol, 94%. Anal. Found (Calc. for
C46H42O2AgP2) C, 68.5 (69.4); H, 5.15 (5.31)%. The
compound was satisfactorily recrystallised from a tolu-
ene–dichloromethane solvent mixture to give poor
quality crystals approximating to the compound as a
1:1 dichloromethane solvate. Anal. Found (Calc. for
C47H44O2AgP2C12) C, 64.0 (64.0); H, 4.69 (5.0)%. IR:
Yield 90%. The product was recrystallised from a
toluene–ethanol solvent mixture and dried in vacuo.
Anal. Found (Calc. for C43H30F13O2AgP2): C, 51.8 (51.9);
2.94 (3.04)%. M.p. 182 °C. IR: 1200, 1237, 1289, 1310,
1356, 1437, 1480, 1659. 1H NMR (CDCl3): 7.43–7.36 (m,
20H, PC6H5), 7.34–7.28 (m, 10H, PC6H5). 13C NMR
(CDCl3): 133.8 (PC6H5), 131.4 (d, J=20 Hz, PC6H5),
130.4 (PC6H5), 128.9 (PC6H5). 19F NMR (CDCl3): −
81.3 (t, J=9.7 Hz, CF3), −116.4 (t, J=12.7 Hz, aCF2),
−122.3 (CF2), −122.9 (CF2), −123.3 (CF2), −126.6
(CF2). 31P NMR (20 °C, CDCl3): 10.2 (br). 109Ag NMR
(−80 °C, CDCl3/CH2Cl2): 823 (t, J=523 Hz).
1
1304, 1435, 1479, 1545, 1574. H NMR (CDCl3): 7.35–
7.15 (m, 30H, PC6H5), 6.65 (m, 2H, O2C6H2), 2.16 (m,
6H, o-CH3), 2.00 (m, 3H, p-CH3). 13C NMR (CDCl3):
176.9 (O2C), 139.5, 134.8 (C6H2Me3), 133.8 (d, J=8.3
Hz, PC6H5, 133.1 (d, J=9.2 Hz, PC6H5), 132.6
(C6H2Me3), 129.8 (PC6H5, 128.7 (d, J=4.6 Hz,
PC6H5), 127.2 (C6H2Me3), 20.9 (C6H2CH3), 19.4
(C6H2CH3). 31P NMR (20 °C, CDCl3): 5.56. 31P NMR
(−80 °C, CDCl3/CH2Cl2): 7.98 (dd, J=497 Hz).
109Ag NMR (−80 °C, CDCl3/CH2Cl2): 895 (t, J=503
Hz).
2.2.16. O,O%-Perfluorooctanoatobis(triphenyl-
phosphine)sil6er(I), Ag(O2CC7F15)(PPh3)2 (16)
Yield 83%. The compound was recrystallised from an
ethanol–toluene solvent mixture. Anal. Found (Cal. for
C44H30F15O2AgP2): C, 51.8 (50.6); H, 3.14 (2.89)%.
M.p. 133 °C. IR: 1206, 1242, 1310, 1437, 1572, 1586,
1
2.2.13. O,O%-Acetatotris(triphenylphosphine)sil6er(I),
Ag(O2CCH3)(PPh3)3 (13)
1692. H NMR (CDCl3): 7.40–7.30 (m, 20H, PC6H5),
7.28–7.22 (m, 10H, PC6H5). 13C NMR (CDCl3): 133.8
(d, J=16.6Hz, PC6H5), 131.9 (d, J=27.6 Hz, PC6H5),
130.2 (PC6H5), 128.8 (d, J=9.2 Hz, PC6H5. 19F NMR
(CDCl3): −81.3 (t, J=9.8 Hz, CF3), −116.4 (t, J=
12.7 Hz, aCF2), −122.1 (CF2), −122.5 (CF2), −122.8
(CF2), −123.1 (CF2), −126.6 (CF2). 31P NMR
(20 °C, CDCl3): 8.9 (br).
Silver acetate (1) (1.67 g, 10 mmol) was added to a
solution of triphenylphosphine (9.18 g, 35 mmol) in 50
cm3 of toluene and the mixture stirred in the absence of
light for 24 h. The pale cream precipitate was filtered in
air and dried in vacuo. Yield 7.82 g, 82%. Anal. Found
(Calc. for C56H48O2AgP3) C, 68.7 (70.52); H, 4.90
(5.07)%. IR: 1325, 1435, 1563. 1H NMR (CDCl3):
7.36–7.02 (m, 45H, C6H5), 2.00 (s, 3H, CH3). 13C NMR
(CDCl3): 174.8 (O2C), 133.7 (d, J=8.3 Hz, PC6H5),
133.2 (d, J=10.1 Hz, PC6H5), 129.6 (PC6H5), 128.5 (d,
J=4.6 Hz, PC6H5), 22.2 (CH3). 31P NMR (20 °C,
CDCl3): 5.79. 31P NMR (−80 °C, CDCl3/CH2Cl2): 7.4
(d, Jꢀ450 Hz), 4.9 (dd, J=256 Hz).
2.3. X-ray crystallography
Crystallographic quality crystals of Ag(O2CC3F7)-
(PPh3)2 (14) were obtained by slow evaporation at r.t.
of a toluene–ethanol solvent mixture. The crystals were
found to be light, air and moisture stable. Data (6102