152
Y. Usui et al. / Inorganica Chimica Acta 309 (2000) 151–154
series II CHN analyzer. Melting points were measured
by a Yamato MP-21, and the values were uncorrected.
Me3SiCF3 (0.50 M THF solution, 0.0550 ml, 0.028
mmol). Yield 8.2 mg (87%). Me3SiOCH(CF3)2 0.020
mmol (71%). This complex was characterized spectro-
scopically. 1H NMR (C6D6): l 0.56 (d, J=10 Hz,
PMe3). 19F{1H} NMR (C6D6): l −29 (br s, CF3).
31P{1H} NMR (C6D6): l −1.8 (br s, PMe3).
2.2. Reactions of Au(OR)L (L=PCy3,
OR=OCH(CF3)2 (1a); OR=OPh (1b); L=PPh3,
OR=OCH(CF3)2 (1c); OR=OPh; L=PMe2Ph,
OR=OCH(CF3)2 (1d); L=PMe3, OR=OCH(CF3)2
(1e)) with Me3SiCF3
2.3. Reactions of cis-AuMe2(OPh)L (L=PMePh2 (3f),
PEt3 (3g), PMe2Ph (3h), PMe3 (3i)) with Me3SiCF3
To a THF (6.5 ml) solution of Au[OCH(CF3)2](PCy3)
(1a) (103 mg, 0.160 mmol) was added Me3SiCF3 (0.50
M THF solution, 0.320 ml, 0.16 mmol). The solution
was stirred at −40°C for 1 h and then at room
temperature (r.t.) for 3 h. After the reaction, GLC
analysis showed the formation of Me3SiOCH(CF3)2
0.125 mmol (78%) [13]. All volatile matters were re-
moved in vacuo to give white powder, which was
washed with cold MeOH, and dried in vacuo. Recrys-
tallization from MeOH gave white crystals of
To cis-AuMe2(OPh)(PMe2Ph) (3h) (59.1 mg, 0.101
mmol) was added Me3SiCF3 (0.50 M THF solution,
0.640 ml, 0.32 mmol) in THF (5 ml). The solution was
stirred at r.t. for 3 h. After the stirring, Me3SiOPh
(0.0972 mmol, 96%) was detected by GLC. After re-
moval of volatile matters in vacuo, the residual solid
was washed with cold hexane to give white powder of
cis-AuMe2(CF3)(PMe2Ph) (4h) [15]. Yield 40.1 mg
(91%). 1H NMR (C6D6): l 0.36 (d, J=9 Hz, 3H,
AuꢀMe trans to P), 1.23 (d, J=10 Hz, 6H, PMe2Ph),
1.66 (qui, J=8 Hz, 3H, AuꢀMe cis to P), 6.8–7.4 (m,
5H, PMe2Ph). 31P{1H} NMR (C6D6): l 4.4 (q, J=6
Hz, PMe2Ph). Anal. Calc. for C11H17AuF3P: C, 30.43;
H, 3.95. Found: C, 30.79; H, 3.74%.
1
Au(CF3)(PCy3) (2a). Yield 20.8 mg (23%). H NMR of
the reaction mixture in C6D6 revealed quantitative for-
mation of 2a. Compound 2a was also prepared from
Au(OPh)(PCy3) (1b) (75.0 mg, 0.136 mmol) and
Me3SiCF3 (0.50 M THF solution, 0.260 ml, 0.13
mmol). Yield 24.0 mg (32%). Me3SiOPh 0.121 mmol
Reactions of other aryloxogold(III) complexes with
various phosphine ligands were carried out
analogously. The yields of the resulting complexes are
summarized below.
1
(89%). H NMR (C6D6): l 0.9–1.5 (m, PCy). 19F{1H}
NMR (C6D6): l −29.1 (d, JFꢀP=41 Hz, CF3). 31P{1H}
NMR (C6D6): l 53.5 (q, JPꢀF=41 Hz, PCy). IR (KBr):
2998, 2903, 1421, 1189, 1120, 992 cm−1. M.p. (dec.):
147–148°C. Anal. Calc. for C19H33AuF3P: C, 41.76; H,
6.09. Found: C, 41.58; H, 6.02%.
cis-AuMe2(CF3)(PMePh2) (4f) was prepared from the
reaction of cis-AuMe2(OPh)(PMePh2) (3f) (12.3 mg,
0.0143 mmol) with Me3SiCF3 (0.33 M THF solution,
1
Reactions of other alkoxo- and aryloxogold(I) com-
plexes with Me3SiCF3 were carried out analogously.
The yields, spectroscopic and physical data of the re-
sulting complexes are summarized below.
0.0440 ml, 0.015 mmol). H NMR yield 0.0142 mmol
(100%). Me3SiOPh 0.0140 mmol (98%).
cis-AuMe2(CF3)(PEt3) (4g) was prepared from the
reaction of cis-AuMe2(OPh)(PEt3) (3g) (11.6 mg,
0.0144 mmol) with Me3SiCF3 (0.33 M THF solution,
Au(CF3)(PPh3) (2b) [14] was prepared from
Au[OCH(CF3)2](PPh3) (1c) (10.3 mg, 0.164 mmol) and
Me3SiCF3 (0.50 M THF solution, 0.640 ml, 0.32
mmol). Yield 18.4 mg (21%). Me3SiOCH(CF3)2 0.118
mmol (72%). Anal. Calc. for C19H15AuF3P: C, 43.20; H,
2.86. Found: C, 43.56; H, 2.52%. Compound 2b was
also prepared from Au(OPh)(PPh3) (1d) (103.0 mg,
0.186 mmol) and Me3SiCF3 (0.50 M THF solution,
0.750 ml, 0.37 mmol). Yield 23.0 mg (23%). Me3SiOPh
0.125 mmol (67%). This complex was characterized
spectroscopically. 1H NMR (C6D6): l 6.9–7.2 (m,
PPh3). 31P{1H} NMR (C6D6): l 38.6 (q, J=46 Hz,
PPh3).
1
0.0440 ml, 0.015 mmol). H NMR yield 0.0142 mmol
(100%). Me3SiOPh 0.0144 mmol (100%)
cis-AuMe2(CF3)(PMe3) (4i) [15] was prepared from
the reaction of cis-AuMe2(OPh)(PMe3) (3i) (115 mg,
0.290 mmol) with Me3SiCF3 (0.50 M THF solution,
1.75 ml, 0.87 mmol). Yield 84.2 mg (78%). Me3SiOPh
1
0.262 mmol (90%). H NMR (C6D6): l 0.50 (d, J=9
Hz, 3H, Au–Me trans to P), 1.60 (d, J=11 Hz, 9H,
PMe3). The methyl group locating cis to the PMe3
ligand was obscure due to overlapping to the incorpo-
rated THF. 19F{1H} NMR (C6D6): l −32.2 (br s,
CF3). 31P{1H} (C6D6): l −3.8 (q, J=6 Hz, PMe3).
Au(CF3)(PMe2Ph) (2c) was prepared from
Au[OCH(CF3)2](PMe2Ph) (1e) (32.5 mg, 0.0647 mmol)
and Me3SiCF3 (0.50 M THF solution, 0.130 ml, 0.065
mmol). Yield 5.4 mg (21%). Me3SiOCH(CF3)2 0.0606
mmol (94%). Anal. Calc. for C9H11AuF3P: C, 26.75; H,
2.74. Found: C, 27.03; H, 2.50%.
2.4. Reactions of Au(OR)L (L=PCy3, OR=
OCH(CF3)2 (1a); L=PPh3, OR=OCH(CF3)2 (1c);
OR=OPh (1d)) with Me3SiCCl3
To
a
benzene (5 ml) solution of Au[OCH-
Au(CF3)(PMe3) (2d) was prepared from Au[OCH-
(CF3)2](PMe3) (1f) (12.1 mg, 0.0275 mmol) and
(CF3)2](PCy3) (1a) (101.0 mg, 0.157 mmol) was added
Me3SiCCl3 (89.2 mg, 0.464 mmol). The solution