Reactivity of [{M(C6F5)2(µ-OH)}2]2- (M ) Pd, Pt)
Organometallics, Vol. 18, No. 7, 1999 1179
(Nujol, cm-1): 3610 (OH str), 785, 770 (Pd-C6F5 str). 1H NMR
((CD3)2CO): δ 6.81 (dd, 2 Ho, J ) 8.8, J ′ ) 5.1), 6.21 (dd, 2
Hm, J ) 8.8, J ′ ) 8.8), -3.08 (s, 1 H, OH). 19F NMR ((CD3)2-
CO): δ -113.3 (d, 4 Fo, J om 33.3), -115.2 (br, 4 Fo), -130.1
(m, 1 Fp, p-FC6H4NH), -166.5 (m, 4 Fm + 2 Fp), -167.8 (m, 4
Fm + 2 Fp).
Sch em e 2
P r ep a r a tion of Com p lexes [{P d (C6F 5)2(µ-NHR)}2]2- (R
) C6H5 (4), C6H4Cl-p (5), C6H4F -p (6)). To a solution of
[NBu4]2[{Pd(C6F5)2(µ-OH)}2] (80 mg; 0.057 mmol) in methanol
(6 mL) was added the corresponding arylamine RNH2 (0.457
mmol for 4, 0.228 mmol for 5 and 6). The solution was stirred
at room temperature for 8 h. The solvent was removed under
vacuum, and the residue was treated with 2-propanol-hexane.
The pale yellow solid was filtered off and air-dried. Complexes
4-6 were recrystallized from dichloromethane-hexane. Com-
plex 4: Yield: 72%. Anal. Calcd for C68H84N4F20Pd2: C, 52.7;
H, 5.5; N, 3.6. Found: C, 52.3; H, 5.7; N, 3.6. Mp: 224 °C dec.
ΛM: 218 S cm2 mol-1. IR (Nujol, cm-1): 775, 770 (Pd-C6F5
1
str). H NMR ((CD3)2CO): δ 6.95 (d, 4 Ho, J ) 7.6), 6.55 (dd,
4 Hm, J ) 7.6), 6.14 (t, 2 Hp, J ) 7.6). 19F NMR ((CD3)2CO): δ
-114.4 (br, 8 Fo), -167.2 (m, 8 Fm), -167.9 (t, 4 Fp, J ) 20.0).
Complex 5: Yield: 69%. Anal. Calcd for C68H82N4Cl2F20Pd2:
C, 50.4; H, 5.1; N, 3.5. Found: C, 50.1; H, 5.4; N, 3.6. Mp:
234 °C dec. ΛM: 214 S cm2 mol-1. IR (Nujol, cm-1): 775, 770
1
Sch em e 3
(Pd-C6F5 str). H NMR ((CD3)2CO): δ 6.93 (d, 4 Ho, J ) 8.6),
6.55 (d, 4 Hm, J ) 8.6). 19F NMR ((CD3)2CO): δ -114.8 (br, 8
Fo), -167.2 (m, 8 Fo + 4 Fp). Complex 6: Yield: 67%. Anal.
Calcd for C68H82N4F22Pd2: C, 51.5; H, 5.2; N, 3.5. Found: C,
51.0; H, 5.5; N, 3.3. Mp: 226 °C dec. ΛM: 220 S cm2 mol-1. IR
(Nujol, cm-1): 775, 770 (Pd-C6F5 str). 1H NMR ((CD3)2CO):
δ 6.90 (dd, 4 Ho, J ) 8.8, J ′ ) 5.0), 6.32 (dd, 4 Hm, J ) 8.8, J ′
) 8.8). 19F NMR ((CD3)2CO): δ -114.2 (br, 8 Fo), -130.6 (m,
2 Fp, p-FC6H4NH), -167.3 (m, 8 Fm + 4 Fp).
P r ep a r a tion of Com p lexes [{P d (C6F 5)2(µ-NHR)}2]2- (R
) C6H4NO2-p (7), C6F 5 (8)). To a solution of [NBu4]2[{Pd-
(C6F5)2(µ-OH)}2] (80 mg; 0.057 mmol) in dichloromethane (6
mL) was added the corresponding arylamine RNH2 (0.114
mmol). The resulting solution was stirred at room temperature
for 30 min and concentrated under vacuum. The addition of
hexane caused the precipitation of an orange or white solid,
which was collected by filtration and air-dried. Complexes 7
and 8 were recrystallized from dichloromethane-hexane.
Complex 7: Yield: 93%. Anal. Calcd for C68H82N6F20O4Pd2: C,
49.8; H, 5.0; N, 5.1. Found: C, 50.1; H, 5.3; N, 5.0. Mp: 231
°C dec. ΛM: 217 S cm2 mol-1. IR (Nujol, cm-1): 3300 (NH str),
10: Yield 76%. Anal. Calcd for C68H74N4F30Pt2: C, 42.8; H,
3.9; N, 2.9. Found: C, 42.5; H, 4.2; N, 3.1. Mp: 256 °C dec.
ΛM: 240 S cm2 mol-1. IR (Nujol, cm-1): 3310 (NH str), 795,
785 (Pt-C6F5 str). 19F NMR ((CD3)2CO): δ -119.4 (d, 8 Fo,
J om ) 27.1, J PtFo ) 495.4), -144.1 (br, 2 Fo, C6F5NH), -161.8
(br, 2 Fo, C6F5NH), -168.0 (m, 8 Fm + 4 Fp), -168.8 (br, 2 Fm,
C6F5NH), -170.8 (br, 2 Fm, C6F5NH), -175.4 (m, 2 Fp, C6F5-
NH).
Rea ction of Com p lex 4 w ith Ca r bon Disu lfid e. To a
solution of 4 (100 mg; 0.064 mmol) in methanol (8 mL) was
added CS2 (1.280 mmol). The solution was stirred at room
temperature for 8 h, and the solvent was removed under
vacuum. The residue was then treated with diethyl ether-
hexane, and a pale yellow solid (complex 11; Scheme 3) was
filtered off and air-dried. Yield: 94%. Anal. Calcd for
1
775, 770 (Pd-C6F5 str). H NMR ((CD3)2CO): δ 7.60 (d, 4 Ho,
J ) 8.9), 7.04 (d, 4 Hm, J ) 8.9), 2.68 (br, 2 H, NH). 19F NMR
((CD3)2CO): δ -115.2 (br, 8 Fo), -165.8 (t, 4 Fp, J om 19.8),
-166.5 (m, 8 Fm). Complex 8: Yield: 92%. Anal. Calcd for
C
68H74N4F30Pd2: C, 47.2; H, 4.3; N, 3.2. Found: C, 46.9; H,
4.4; N, 3.4. Mp: 246 °C dec. ΛM: 219 S cm2 mol-1. IR (Nujol,
cm-1): 3310 (NH str), 780, 770 (Pd-C6F5 str). 1H NMR ((CD3)2-
CO): δ 2.25 (br, 2 H, NH). 19F NMR ((CD3)2CO): δ -115.1 (d,
8 Fo, J ) 27.9), -146.1 (br, 2 Fo, C6F5NH), -164.1 (br, 2 Fo,
C6F5NH), -165.8 (t, 4 Fp, J ) 19.8), -166.7 (m, 8 Fm), -169.2
(br, 2 Fm, C6F5NH), -171.4 (br, 2 Fm, C6F5NH), -178.8 (m, 2
Fp, C6F5NH).
C
34H42N2S2F10Pd: C, 49.4; H, 4.9; N, 3.3; S, 7.5. Found: C,
49.2; H, 5.0; N, 3.2; S, 7.7. Mp: 116 °C dec. ΛM: 107 S cm2
P r ep a r a tion of Com p lexes [{P t(C6F 5)2(µ-NHR)}2]2- (R
) C6H4NO2-p (9), C6F 5 (10)). To a solution of [NBu4]2[{Pt
(C6F5)2(µ-OH)}2] (80 mg; 0.051 mmol) in methanol (6 mL) was
added the arylamine RNH2 (0.102 mmol). The solution was
boiled under reflux for 3 h. The solvent was removed under
vacuum, and the residue was treated with dichloromethane-
hexane. The orange or white solid was filtered off and air-
dried. Complexes 9 and 10 were recrystallized from dichlo-
romethane-hexane. Complex 9: Yield: 90%. Anal. Calcd for
mol-1. IR (Nujol, cm-1): 3230 (NH str), 782, 774 (Pd-C6F5 str),
1538 (CN str), 978 (CS str). H NMR ((CD3)2CO): δ 10.52 (br,
1
1 H, NH), 7.69 (d, 2Ho, J om ) 9.5), 7.36 (dd, 2Hm, J mp ) 5.38),
7.18 (t, 1Hp). 19F NMR ((CD3)2CO): δ -111.7 (d, 4 Fo, J om
27.4), -165.8 (t, 2 Fp, J mp ) 18.1), -166.7 (m, 4 Fm).
)
P r ep a r a tion of Com p lexes 12 a n d 13. To a solution of
[NBu4]2[Pd2(C6F5)4(µ-OH)2] (0.1 g, 0.0714 mmol) in methanol
(6 mL) was added malononitrile or methyl cyano acetate
(0.1428 mmol). The resulting solution was stirred at room
temperature for 1 h, and the solvent was then partially
evaporated under reduced pressure. On addition of water the
white complexes 12 and 13 precipitated and were filtered off
C
68H82N6F20O4Pt2: C, 44.9; H, 4.9; N, 4.4. Found: C, 44.9; H,
5.0; N, 4.4. Mp: 258 °C dec. ΛM: 232 S cm2 mol-1. IR (Nujol,
cm-1): 800, 790 (Pt-C6F5 str). 1H NMR ((CD3)2CO): δ 7.63
(d, 4 Ho, J ) 8.9), 7.18 (d, 4 Hm, J ) 8.9). 19F NMR ((CD3)2-
CO): δ -119.7 (br, 8 Fo), -167.9 (m, 8 Fm + 4 Fp). Complex
and air-dried. Complex 12: yield 89%; mp 169 °C dec; ΛM
)