[Cu(PNH2)2]TfO (4). To an acetonitrile solution (20 mL) of
[Cu(NCMe)4]TfO (0.25 mmol; 0.09 g) was added PNH2
(0.5 mmol; 0.14 g) and after 15 min of stirring the solvent was
evaporated to ca. 5 mL. Addition of diethyl ether (20 mL)
led to precipitation of complex 4 as a white solid. Yield: 61%.
Mass spectrum: [M]ϩ at m/z = 617 (100%). Anal. Calcd. for:
C37H32CuF3N2O3P2S (4): C, 57.95; H, 4.2; N, 3.65; S, 4.2.
Found: C, 57.75; H, 4.05; N, 3.95; S, 4.3%. 31P{1H} NMR
C38H32Cu2F6N2O6P2S2 (9): C, 46.6; H, 3.3; N, 2.85; S, 6.55.
Found: C, 46.7; H, 3.25; N, 2.75; S, 6.7%. 31P{1H} NMR
1
(CDCl3) δ: Ϫ10.8 (s). 19F NMR (CDCl3), δ: Ϫ78.25 (s). H
NMR (CDCl3), δ: 6.68–7.47 [m, 28H, aromatic protons],
∼5.1 [m, 4H, NH2]. ΛM = 124 ΩϪ1 cm2 molϪ1
.
[AuM(PNH2)2](TfO)2 (M ؍
Ag (10), Cu (11)). Method 1. A
dichloromethane solution of complex 1 (0.2 mmol, 0.18 g) was
added to a solution of 0.2 mmol of AgTfO (0.05 g) in diethyl
ether (10) or [Cu(NCMe)4]TfO (0.07 g) in acetonitrile (11).
After 15 min of stirring at room temperature the solvent was
evaporated to ca. 5 mL and addition of diethyl ether (20 mL)
led to precipitation of complexes 10 or 11 as white solids. Yield:
83 (10); 86% (11).
1
(CDCl3), δ: Ϫ11.7 (s). 19F NMR (CDCl3), δ: Ϫ78.25 (s). H
NMR (CDCl3), δ: 7.13–7.4 [m, 28H, aromatic protons], ∼4.9
[m, 4H, NH2]. ΛM = 70 ΩϪ1 cm2 molϪ1
.
[Au(PN᎐CMe )] (ClO ) (5). To a solution of AgClO (0.25
᎐
2
2
4
2
4
mmol; 0.05 g) in acetone was added [AuCl(PNH2)] (0.25 mmol;
0.13 g). After 3 h of stirring the AgCl formed was filtered
off and the resulting solution was concentrated in vacuum.
Addition of 20 mL of diethyl ether led to precipitation of 5 as a
white solid. Yield: 86%. Anal. Calcd. for: C42H40Au2Cl2N2O8P2
(5): C, 41.1; H, 3.3; N, 2.3. Found: C, 40.9; H, 3.35; N, 2.3%.
Method 2. To a solution of [Au(tht)2]TfO (0.2 mmol, 0.10 g)
in 20 mL of dichloromethane was added 0.2 mmol of 4 (0.15 g)
or 2 (0.16 g). The solution was stirred for 15 min and then
concentrated in vacuum. Addition of diethyl ether (20 mL) led
to the precipitation of complexes 10 or 11 as white solids. Yield:
90 (10); 78% (11). Anal. Calcd. for: C38H32AgAuF6N2O6P2S2
(10): C, 39.45; H, 2.8; N, 2.4; S, 5.55. Found: C, 39.55; H, 2.65;
N, 2.45; S, 5.65%. C38H32AgCuF6N2O6P2S2 (11): C, 41.0; H, 2.9;
N, 2.5; S, 5.75. Found: C, 40.7; H, 2.95; N, 2.85; S, 5.65%.
31P{1H} NMR (CDCl3): δ: (10) 31.1 (s); (11) 29.5 (s). 19F NMR
1
31P{1H} NMR (HDA), δ: 20.5 (s). H NMR (HDA), δ: 7.13–
7.93 [m, 28H, aromatic protons], 2.06 [m, 12H, Me]. ΛM
=
125 ΩϪ1 cm2 molϪ1
.
[Au(PNH2)]2(ClO4)2 (6). To a solution of AgClO4 (0.25
mmol; 0.05 g) in dichloromethane/toluene (1/1) was added
[AuCl(PNH2)] (0.25 mmol; 0.13 g). After 3 h of stirring the
AgCl formed was filtered off and the resulting solution was
concentrated in vacuum. Addition of 20 mL of diethyl ether led
to precipitation of 6 as a white solid. Yield: 95%. Anal. Calcd.
for: C36H32Au2Cl2N2O8P2 (6): C, 37.7; H, 2.8; N, 2.45. Found:
C, 37.75; H, 2.9; N, 2.5%. 31P{1H} NMR (CDCl3), δ: 17.1 (s).
1H NMR (CDCl3), δ: 6.45–7.72 [m, 28H, aromatic protons],
1
(CDCl3), δ: (10 and 11) Ϫ78.25 (s). H NMR (CDCl3), δ: (10)
6.73–7.65 [m, 28H, aromatic protons], 5.18 [s, 4H, NH2]; (11)
6.74–7.59 [m, 28H, aromatic protons], 5.47 [s, 4H, NH2]. ΛM
=
124 (10); 105 ΩϪ1 cm2 molϪ1 (11).
[Au(PNH2)3]ClO4 (12). To
a dichloromethane solution
(20 mL) of [Au(tht)2]ClO4 (0.2 mmol, 0.10 g) was added PNH2
(0.6 mmol; 0.17 g) and after 30 min of stirring at room tempera-
ture the solvent was evaporated to ca. 5 mL. Addition of diethyl
ether (20 mL) led to precipitation of complex 12 as a white
solid. Yield: 77%. Anal. Calcd. for: C55H48AuF3N3O3P3S (12):
C, 56.1; H, 4.1; N, 3.55; S, 2.7. Found: C, 54.8; H, 4.4; N, 3.35;
S, 2.6%. 31P{1H} NMR (CDCl3), 298 K, δ: 26.0 (m); 223 K,
δ: 28.8 (s). 19F NMR (CDCl3), δ: Ϫ78.25 (s). 1H NMR (CDCl3),
δ: 6.57–7.37 [m, 42H, aromatic protons], 4.74 [m, 6H, NH2].
4.94 [s, 4H, NH2]. ΛM = 120 ΩϪ1 cm2 molϪ1
.
[Ag(PNH2)]2A2 (A ؍
TfO (7), ClO4 (8)). Method 1. To a
diethyl ether solution (20 mL) of 0.5 mmol of AgA (A = TfO,
0.13 g; A = ClO4, 0.14 g) was added PNH2 (0.5 mmol, 0.14 g)
and a white precipitate immediately started to form. After 2 h
of stirring at room temperature the precipitation was complete;
complexes 7 and 8 were obtained as white solids that were then
filtered off. Yield: 72 (7), 97% (8).
ΛM = 73 ΩϪ1 cm2 molϪ1
.
[Ag(PNH2)3]ClO4 (13). To a solution of 0.2 mmol of AgClO4
(0.04 g) in 20 mL of diethyl ether was added PNH2 (0.6 mmol;
0.17 g); a white precipitate immediately appeared. After 3 h of
stirring the precipitation was complete and the white solid was
filtered off. Yield: 88%. Anal. Calcd. for: C54H48AgClN3O4P3
(13): C, 62.4; H, 4.65; N, 4.05. Found: C, 61.7; H, 5.05;
N, 3.85%. 31P{1H} NMR (HDA): 298 K, δ: Ϫ3.6 (m); 223 K,
Method 2. To a solution of 0.2 mmol of AgA (A = TfO, 0.05
g; A = ClO4, 0.04 g) in acetone was added 0.2 mmol of 2 (0.16 g)
(7) or 3 (0.15 g) (8). After 15 min of stirring the solution was
concentrated in vacuum and addition of 20 mL of diethyl ether
led to the precipitation of complexes 7 and 8 as white solids.
Yield: 70 (7), 85% (8). Mass spectra: [M A]ϩ at m/z = 919 (6%,
ؒ
7); 869 (6%, 8). Anal. Calcd. for: C38H32Ag2F6N2O6P2S2 (7): C,
42.7; H, 3.0; N, 2.6; S, 6.0. Found: C, 42.6; H, 3.15; N, 2.35;
S, 6.05%. C36H32Ag2Cl2N2O8P2 (8): C, 44.6; H, 2.35; N, 2.9.
Found: C, 44.35; H, 3.25; N, 3.1%. 31P{1H} NMR (HDA): 298
K, δ: (7) Ϫ0.8 (m); (8) Ϫ0.8 (m); 223 K, δ: (7) Ϫ2.10 (broad
doublet); (8) Ϫ2.4 (broad doublet). 19F NMR (HDA), δ: (7)
Ϫ78.25 (s). 1H NMR (HDA), 223 K, δ: (7) 6.71–7.66 [m,
28H, aromatic protons], 5.67 [s, 4H, NH2]; (8) 6.72–7.64
[m, 28H, aromatic protons], 5.68 [s, 4H, NH2]. ΛM = 128 (7);
117 ΩϪ1 cm2 molϪ1 (8).
1
δ: Ϫ3.5 [J(109Ag–P) = 365; J(107Ag–P) = 320 Hz]. H NMR
(HDA), δ: 6.75–7.51 [m, 42H, aromatic protons], 4.72 [s, 6H,
NH2]. ΛM = 81 ΩϪ1 cm2 molϪ1
.
[Cu(PNH2)3]TfO (14). To an acetonitrile solution (20 mL)
of [Cu(NCMe)4]TfO (0.2 mmol, 0.07 g) was added PNH2
(0.6 mmol; 0.17 g) and after 30 min of stirring the solvent was
evaporated to ca. 5 mL. Addition of diethyl ether (20 mL) led to
precipitation of complex 14 as a white solid. Yield: 70%. Anal.
Calcd. for: C55H48CuF3N3O3P3S (14): C, 63.25; H, 4.65; N, 4.0;
S, 3.05. Found: C, 63.0; H, 4.35; N, 3.75; S, 2.85%. 31P{1H}
NMR (CDCl3), 298 K, δ: Ϫ9.1 (m); 223 K, δ: Ϫ8.3 (s). 19F
[Cu(PNH2)]2(TfO)2 (9). Method 1. To an acetonitrile solution
(20 mL) of [Cu(NCMe)4]TfO (0.5 mmol; 0.19 g) was added
PNH2 (0.5 mmol; 0.14 g). After 15 min of stirring at room
temperature the solvent was evaporated to ca. 5 mL and
addition of diethyl ether (20 mL) led to precipitation of 9 as a
white solid. Yield: 70%.
Method 2. To a solution of [Cu(NCMe)4]TfO (0.2 mmol,
0.07 g) in acetonitrile was added 0.2 mmol of 4 (0.15 g). After
15 min of stirring the solution was concentrated in vacuum
and addition of 20 mL of diethyl ether led to the precipitation
of complex 9 as a white solid. Yield: 65%. Anal. Calcd. for:
1
NMR (CDCl3), δ: Ϫ78.25 (s). H NMR (CDCl3), δ: 6.64–7.31
[m, 42H, aromatic protons], 4.65 [m, 6H, NH2]. ΛM = 73 ΩϪ1
cm2 molϪ1
.
Crystal structure determinations
The crystals were mounted in inert oil on a glass fibre and
transferred to the cold gas stream of a Siemens P4 or Siemens-
Smart 1000-CCD (5) diffractometers. Data were collected using
monochromated Mo Kα radiation (λ = 0.71073 Å). Absorption
1324
J. Chem. Soc., Dalton Trans., 2002, 1319–1326