Perfluoroalkyl-Functionalized Metal Complexes
(89%) Anal. Calcd for C74H60Cl2F68NiP2Si4: C 34.92, H 2.38, F
50.76. Found: C 35.11, H 2.51, F 50.55. H NMR (200 MHz,
Found C 31.04, H 1.89, F 54.29. 1H NMR (200 MHz, C6D6/FC-72
1:1 v/v): δ 0.00 (s, 12H), 0.83 (br, 16H), 1.84 (br, 16H), 7.15 (br,
8H), 7.96 (br, 8H).
cis-PtCl2[P(4-C6H4-SiMe2CH2CH2CF3)3]2 (6a). Compound 2a
(0.25 g; 0.35 mmol) and PtCl2(COD) (64.6 mg; 0.17 mmol) yielded
0.24 g (82%) of a white solid. Anal. Calcd for C66H84Cl2F18P2-
PtSi6: C 46.20, H 4.93, P 3.61. Found: C 46.16, H 4.98, P 3.68.
1H NMR (200 MHz, CDCl3): δ 0.33 (s, 36H), 0.96 (m, 12H), 1.96
(m, 12H), 7.28 (m, 12H), 7.45 (m, 12H).
cis-PtCl2[P(4-C6H4-SiMe2CH2CH2C6F13)3]2 (6b). Compound 2b
(0.53 g; 0.36 mmol) and PtCl2(COD) (67.0 mg; 0.18 mmol) yielded
0.53 g (91%) of a white solid. Anal. Calcd for C96H84Cl2F78P2-
PtSi6: C 35.85, H 2.63, P 1.93. Found: C 35.70, H 2.71, P 1.85.
1H NMR (200 MHz, CDCl3): δ 0.29 (s, 36H), 0.94 (m, 12H), 1.92
(m, 12H), 7.46 (m, 24H).
General Procedure for Synthesis of 7. A solution of 1 in CH2-
Cl2 was added to a solution of [Ni(MeCN)6](BF4)2‚1/2MeCN in
MeCN. After the reaction mixture stirred for 2 h, all volatiles were
evaporated in vacuo. The residue was dissolved in CH2Cl2, filtered,
and evaporated to dryness.
1
CDCl3): δ 0.37 (s, 24H), 1.03 (m, 8H), 2.07 (m, 12H), 7.61 (m,
8H), 7.98 (m, 8H). 31P NMR (81 MHz, CDCl3): δ 58.1. 19F NMR
(282.4 MHz, CDCl3): δ -126.6 (m, 8F), -123.5 (m, 8F), -123.2
(m, 8F), -122.4 (m, 24 F), -116.4 (m, 8F), -81.3 (m, 12 F).
3e. Compound 1e (2.29 g; 0.69 mmol) dissolved in EtOH/
CF3C6H5 (100 mL; 1:1 v/v) and NiCl2‚6H2O (163 mg; 0.69 mmol)
yielded 2.13 g of a red waxy solid (89%). Anal. Calcd for C94H64-
Cl2F104NiP2Si4: C 32.51, H 1.86, P 1.78. Found: C 32.38, H 1.94,
1
P 1.88. H NMR (200 MHz, CDCl3): δ 0.34 (br, 12H), 1.06 (br,
16 H), 2.02 (br, 20 H), 7.4-8.2 (br, 16H). 31P NMR (81 MHz,
CDCl3): δ 58.0.
3f. Compound 1f (1.68 g; 0.36 mmol) dissolved in CF3C6H5 and
NiCl2‚6H2O (85 mg; 0.36 mmol) yielded 1.50 g of a red oil (87%).
Anal. Calcd for C122H68Cl2F156NiP2Si4: C 30.52, H 1.43, P 1.29.
Found: C 30.32, H 1.36, P 1.42. 1H NMR (200 MHz, C6D6/FC-72
1:1 v/v): δ 1.01 (br, 24H), 1.96 (br, 28H), 7.2-8.2 (br, 16H). 31
NMR (81 MHz, CDCl3/CF3C6H5 1:1 (v/v)): δ 57.8.
P
General Procedure for Synthesis of 4. A solution of 1 in CH2-
Cl2 (1a, 1c) or PFMCH (1f) was added to a solution of PdCl2(COD)
in CH2Cl2. After the reaction mixture stirred overnight, all solvent
was evaporated in vacuo.
7a. Compound 1a (0.10 g; 0.14 mmol) and [Ni(MeCN)6](BF4)2‚
1/2MeCN (35 mg; 70 µmol) yielded 0.10 g (89%) of a yellow solid.
Anal. Calcd for C76H112B2F8NiP4Si8: C 56.82, H 7.03, P 7.71.
Found: C 56.70, H 6.92, P 7.56. 1H NMR (200 MHz, CD3CN): δ
0.36 (s, 72H), 2.71 (m, 8H), 7.06 (m, 16H), 7.51 (m, 16H). 31P
NMR (81 MHz, CD3CN): δ 54.5.
4a. Compound 1a (0.16 g; 0.22 mmol) and PdCl2(COD) (64 mg;
0.22 mmol) yielded 0.16 g (81%) of a yellow solid. Anal. Calcd
for C38H56Cl2P2PdSi4: C 52.80, H 6.53, P 7.17. Found: C 52.55,
1
H 6.46, P 7.25. H NMR (200 MHz, CDCl3): δ 0.27 (s, 24H),
7b. Compound 1b (0.28 g; 0.26 mmol) and [Ni(MeCN)6](BF4)2‚
1/2MeCN (65 mg; 0.13 mmol) yielded 0.27 g (87%) of an orange
oil. Anal. Calcd for C132H224B2F8NiP4Si8: C 66.28, H 9.44, P 5.18.
Found: C 66.20, H 9.35, P 5.29. 1H NMR (200 MHz, CDCl3): δ
0.24 (s, 48H), 0.73 (m, 16H), 0.87 (br, 16H), 1.25 (br, 96H), 2.92
(m, 8H), 7.1-7.5 (m, 32H). 31P NMR (81 MHz, CDCl3): δ 54.9.
7c. Compound 1c (0.68 g; 0.34 mmol) and [Ni(MeCN)6](BF4)2‚
1/2MeCN (85 mg; 0.17 mmol) yielded 0.67 g (93%) of a yellow
solid, which was recrystallized from MeCN and hexane. Anal. Calcd
for C132H120B2F112NiP4Si8: C 37.19, H 2.84, P 2.91. Found: C
2.44 (m, 4H), 7.59 (m, 8H), 7.82 (m, 8H). 31P NMR (81 MHz,
CDCl3): δ 64.7.
4c. Compound 1c (0.27 g; 0.13 mmol) and PdCl2(COD) (38 mg;
0.13 mmol) yielded 0.27 g (95%) of a yellow solid. Anal. Calcd
for C66H60Cl2F52P2PdSi4: C 36.15, H 2.76, P 2.83. Found: C 36.26,
1
H 2.70, P 2.99. H NMR (200 MHz, CDCl3): δ 0.35 (s, 24H),
1.01 (m, 8H), 2.02 (m, 8H), 2.50 (m, 4H), 7.61 (m, 8H), 7.90 (m,
8H). 31P NMR (81 MHz, CDCl3): δ 64.5. 19F NMR (282.4 MHz,
CDCl3): δ -126.7 (m, 8F), -123.6 (m, 8F), -123.4 (m, 8F),
-122.5 (m, 8F), -116.4 (m, 8F), -81.4 (m, 12F).
1
37.09, H 2.85, P 3.04. H NMR (200 MHz, CD3CN): δ 0.36 (s,
4f. Compound 1f (0.21 g; 44 µmol) and PdCl2(COD) (13 mg;
44 µmol) yielded 0.21 g (90%) of a yellow oil. Anal. Calcd for
48H), 1.05 (m, 16H), 2.08 (m, 16H), 2.71 (m, 8H), 6.9-7.6 (m,
32H). 31P NMR (81 MHz, CD3CN): δ 54.5 (s, 3P). 19F NMR (282
MHz, CD3CN): δ -150.7 (m, 8F), -125.7 (m, 16F), -122,4 (m,
32F), -121.4 (m, 16F), -115.1 (m, 16F), -80.6 (m, 24F).
General Procedure for Synthesis of 8. A solution of 1 in CH2-
Cl2 was added to a solution of [Pd(MeCN)4](BF4)2 in MeCN. After
the reaction mixture for 2 h, all volatiles were evaporated in vacuo.
The residue was dissolved in CH2Cl2, filtered, and evaporated to
dryness.
8a. Compound 1a (217 mg; 0.30 mmol) and [Pd(MeCN)4](BF4)2
(67 mg; 0.15 mmol) yielded 240 mg (97%) of a light yellow solid.
Anal. Calcd for C76H112B2F8P4PdSi8: C 55.18, H 6.82, P 7.49.
Found: C 54.94, H 6,73, P 7.58. 1H NMR (200 MHz, CD3CN): δ
0.20 (s, 72 H), 3.02 (m, 8H), 7.20 (m, 16H), 7.41 (m, 16H). 31P
NMR (81 MHz, CDCl3): δ 56.5.
C
122H68Cl2F156P2PdSi4: C 30.22, H 1.41, P 1.28. Found: C 30.25,
1
H 1.49, P 1.41. H NMR (200 MHz, C6D6/PFMCH 1:1 (v/v)): δ
0.86 (br, 24H), 1.85 (br, 28H), 6.8-8.0 (br, 16H). 31P NMR (81
MHz, C6D6/PFMCH 1:1 (v/v)): δ 62.2.
General Procedure for Synthesis of 5. A solution of 1 equiv
of 1 or 2 equiv of monophosphine in CH2Cl2 was added to a solution
of 1 equiv of PtCl2(COD) in CH2Cl2. After the reaction mixture
stirred overnight, all solvent was evaporated in vacuo.
5a. Compound 1a (0.15 g; 0.22 mmol) and PtCl2(COD) (81 mg;
0.22 mmol) yielded 0.19 g (92%) of a white solid. Anal. Calcd for
C38H56Cl2P2PtSi4: C 47.88, H 5.92, P 6.50. Found: C 47.90, H
1
6.05, P 6.39. H NMR (200 MHz, CDCl3): δ 0.30 (s, 36H), 2.37
(m, 4H), 7.60 (m, 8H), 7.81 (m, 8H).
5c. Compound 1c (0.45 g; 0.22 mmol) and PtCl2(COD) (84 mg;
0.22 mmol) yielded 0.46 g (93%) of a white solid. Anal. Calcd for
C66H60Cl2F52P2PtSi4: C 34.75, H 2.65, P 2.72. Found: C 34.61, H
8c. Compound 1c (294 mg; 0.146 mmol) and [Pd(MeCN)4](BF4)2
(32.4 mg; 73 µmol) yielded 292 mg (93%) of a light yellow solid.
Anal. Calcd for C132H120B2F112P4PdSi8: C 36.78, H 2.81, P 2.87.
Found: C 36.91, H 2.90, P 2.97. 1H NMR (200 MHz, CDCl3): δ
0.29 (s, 48H), 1.07 (m, 16H), 2.10 (m, 16H), 2.92 (m, 8H), 6.9-
7.6 (m, 32H). 31P NMR (81 MHz, CDCl3): δ 56.8. 19F NMR (282
MHz, CD3CN): δ -155.2 (m, 8F), -130.1 (m, 16F), -126.8 (m,
32F), -125.9 (m, 16F), -199.5 (m, 16F), -85.1 (m, 24F).
Solubility Studies of NiCl2(dppe) and 3. Saturated solutions
were prepared by stirring the nickel complex in the appropriate
solvent for 30 min at 25 °C. A sample was taken after the mixture
1
2.70, P 2.80. H NMR (200 MHz, CDCl3): δ 0.34 (s, 24H), 1.00
(m, 8H), 2.02 (m, 8H), 2.36 (m, 4H), 7.56 (m, 8H), 7.85 (m, 8H).
19F NMR (282.4 MHz, CDCl3): δ -126.7 (m, 8F), -123.6 (m,
8F), -123.4 (m, 8F), -122.5 (m, 8F), -116.4 (m, 8F), -81.4 (m,
12F).
5e. Compound 1e (0.41 g; 0.12 mmol) and PtCl2(COD) (46 mg;
0.12 mmol) yielded 0.39 g (91%) of a waxy white-yellow solid.
Anal. Calcd for C94H64Cl2F104P2PtSi4: C 31.28, H 1.79, F 54.74.
Inorganic Chemistry, Vol. 42, No. 6, 2003 2123