1816 Organometallics, Vol. 21, No. 9, 2002
Hahn et al.
py). 13C NMR (50 MHz, CD3OD/CD2Cl2): δ 0.5 (s, 1J C-Pt ) 651
Rea ction of [P t(P NP )(CH2dCHR)](BF 4)2 w ith H2O.
Gen er a l P r oced u r e. A mixture of 0.230 mmol of the alkene
complex in 5 mL of CH2Cl2 with 4 equiv of H2O and 2 equiv of
NaHCO3 was stirred for 1 h at 0 °C. The gray precipitated
NaBF4 was filtered off. The product was precipitated by
dropwise addition of diethyl ether. The product was filtered
off, washed with diethyl ether, and dried under vacuum.
2
4
Hz, PtCH2), 46.5 (ps.t, J C-P + J C-P ) 16.4 Hz, PCH2), 51.4
3
5
(s, OCH3), 77.9 (s, CH2), 124.0 (ps.t, J C-P + J C-P ) 4.3 Hz,
py-3,5), 128.3 (ps.t, 1J C-P + 3J C-P ) 27.3 Hz, PPhi), 130.6 (ps.t,
2
3J C-P + 5J C-P ) 5.5 Hz, Phm), 131.3 (s, Php), 134.2 (ps.t, J C-P
4
+ J C-P ) 7.3 Hz, Pho), 140.2 (s, py-4), 160.8 (s, py-2,6). 31P
1
NMR (162 MHz, CD2Cl2): δ 29.9 (s, J P-Pt ) 3020 Hz).
[P t(P NP )(CH2CH(Me)OMe)]BF 4 (9). Yield: 162 mg (0.195
[P t(P NP )(CH2CH2OH)]BF4 (14)/[{P t(P NP )(CH2CH2)}2O]-
(BF 4)2 (15). Yield: 160 mg (0.200 mmol, 87%, based on Pt),
1
mmol, 85%), white solid. H NMR (200 MHz, CD2Cl2): δ 0.65
3
white solid. 1H NMR (200 MHz, CD2Cl2): 14: δ 2.08 (m, 2J H-Pt
(d, J H-H ) 6.0, 3H, CH3), 1.79 (m, 1H, PtCH2), 2.26 (m, 1H,
2
PtCH2), 2.72 (s, 3H, OCH3), 2.97 (m, 1H, CHO), 4.42 (ps.t, 4H,
) 88 Hz, 2H, PtCH2), 3.34 (m, 2H, CH2O), 4.46 (ps.t, J H-P
+
4
2J H-P + J H-P ) 4.6 Hz, PCH2), 7.48-7.98 (m, 22H, Ph, py),
4J H-P ) 4.8 Hz, 4H, PCH2), 7.30-7.80 (m, 23H, Ph, py). 15: δ
1.85 (m, 2J H-Pt ) 93 Hz, 2H, PtCH2), 2.66 (m, 2H, CH2O), 4.39
3
8.03 (t, J H-H ) 8.0 Hz, 1H, py-4). 13C NMR (50 MHz, CD3-
1
(ps.t, J H-P + 4J H-P ) 4.6 Hz, 4H, PCH2), 7.30-7.80 (m, 23H,
2
OD): δ 4.6 (s, J C-Pt ) 651 Hz, PtCH2), 19.9 (s, CH3), 42.3 (s,
OCH3), 42.8 (m, PCH2), 79.3 (s, CH), 120.2 (br, py-3,5), 126.9
Ph, py).
3
5
(ps.t, J C-P + J C-P ) 5.5 Hz, Phm,m′), 129.6 (s, Php), 129.7 (s,
[P t(P NP )(CH2CH(Me)OH)]BF 4 (16). Yield: 150 mg (0.184
mmol, 80%), white solid. Anal. Calcd for C34H34BF4NOP2Pt‚
2CH2Cl2: C, 43.84; H, 3.88; N, 1.42. Found: C, 43.42; H, 3.81;
Php′), 130.6 (ps.t, 2J C-P + 4J C-P ) 6.1 Hz, Pho), 130.6 (ps.t, 2J C-P
4
+ J C-P ) 6.9 Hz, Pho′), 137.7 (s, py-4), 157.6 (s, py-2,6).
[P t(P NP )(CH2CH(Et)OMe)]BF4 (10). Yield: 151 mg (0.179
1
3
N, 1.41. H NMR (200 MHz, CD2Cl2): δ 0.71 (d, J H-H ) 6.0
1
mmol, 78%), white solid. H NMR (200 MHz, CD2Cl2): δ 0.35
Hz, 3H, CH3), 0.96 (d, 3J H-H ) 4.4 Hz, 1H, OH), 2.04 (m, 2J H-Pt
(t, 3J H-H ) 7.4, 3H, CH3), 0.98 (m, 1H, CH2), 1.18 (m, 1H, CH2),
2
) 79 Hz, 2H, PtCH2), 3.55 (m, 1H, CHO), 4.43 (ps.t, J H-P
+
1.80 (m, 1H, PtCH2), 2.22 (m, 1H, PtCH2), 2.64 (m, 1H, CHO),
4J H-P ) 4.6 Hz, 4H, PCH2), 7.40-7.98 (m, 21H, Ph, py), 8.02
2
2.73 (s, 3H, OCH3), 4.42 (ps.t, J H-P
+
4J H-P ) 4.8 Hz, 4H,
(t, J H-H ) 7.3 Hz, 1H, py-4). 13C NMR (50 MHz, CD2Cl2): δ
3
3
PCH2), 7.48-7.98 (m, 22H, Ph, py), 8.03 (t, J H-H ) 7.3 Hz,
1H, py-4).
12.8 (s, 1J C-Pt ) 666 Hz, PtCH2), 26.8 (s, 3J C-Pt ) 46 Hz, CH3),
46.6 (ps.t, 2J C-P + 4J C-P ) 16.2 Hz, PCH2), 71.9 (s, CH), 123.4
(ps.t, 3J C-P + 5J C-P ) 4.8 Hz, py-3,5), 130.0 (ps.t, 3J C-P + 5J C-P
[P t(P NP )(CH2CH(P h )OMe)]BF4 (11). Yield: 181 mg (0.202
mmol, 88%), white solid. Anal. Calcd for C40H38BF4NOP2Pt:
C, 53.83; H, 4.29; N, 1.57. Found: C, 53.71; H, 4.38; N, 1.56.
) 5.1 Hz, Phm), 131.8 (s, Php), 133.6 (ps.t, J C-P + 4J C-P ) 7.3
2
Hz, Pho), 139.7 (s, py-4), 159.0 (s, py-2,6). 31P NMR (162 MHz,
2
1H NMR (200 MHz, CD2Cl2): δ 2.02 (m, J H-Pt ) 80 Hz, 2H,
1
CD2Cl2): δ 29.4 (s, J P-Pt ) 3033 Hz).
PtCH2), 2.60 (s, 3H, OCH3), 3.69 (m, 1H, CHO), 4.42 (m, 4H,
PCH2), 6.60 (m, 2H, Ph), 7.09 (m, 3H, CPh), 7.54-7.66 (m,
[P t(P NP )(CH2CH(Et)OH)]BF 4 (17). Yield: 152 mg (0.184
1
mmol, 80%), white solid. H NMR (200 MHz, CD2Cl2): δ 0.40
3
8H, PPh), 7.79-7.91 (m, 14H, PPh, py), 8.00 (t, 1H, J H-H
)
)
)
(t, 3J H-H ) 7.3 Hz, 3H, CH3), 0.93 (d, 3J H-H ) 4.4 Hz, 1H, OH),
0.93 (m, 1H, CH2), 1.13 (m, 1H, CH2), 2.06 (m, 2J H-Pt ) 84 Hz,
2H, PtCH2), 3.20 (br, 1H, CHO), 4.43 (m, 4H, PCH2), 7.40-
2
7.4 Hz, py-4). 13C NMR (75 MHz, CD2Cl2): δ 11.0 (t, J C-P
1
3
5
4.4 Hz, J C-Pt ) 658 Hz, PtCH2), 46.2 (ps.t, J C-P + J C-P
2
17.3 Hz, PCH2), 56.0 (s, OCH3), 87.9 (s, J C-Pt ) 26 Hz CH),
8.03 (m, 23H, Ph, py). 13C NMR (50 MHz, CD2Cl2): δ 9.5 (s,
3
123.3 (ps.t, J C-P
+
5J C-P ) 5.0 Hz, py-3,5), 125.9 (s, CPh),
2
PtCH2), 9.5 (s, CH3), 33.0 (s, CH2), 46.7 (ps.t, J C-P + 4J C-P
)
127.0 (s, CPh), 127.4 (ps.t, 1J C-P + 3J C-P ) 28.1 Hz, PPhi), 127.7
16.5 Hz, PCH2), 77.2 (t, 2J C-P ) 7.4 Hz, CH), 123.4 (ps.t, 3J C-P
1
(ps.t, J C-P
+
3J C-P ) 28.2 Hz, PPhi′), 128.4 (s, CPh), 129.7
+ 5J C-P ) 4.7 Hz, py-3,5), 130.0 (ps.t, J C-P + 5J C-P ) 5.4 Hz,
3
(ps.t, 3J C-P + 5J C-P ) 5.3 Hz, PPhm), 129.8 (ps.t, 3J C-P + 5J C-P
) 5.8 Hz, PPhm′), 132.5 (s, PPhp), 132.6 (s, PPhp′), 133.5 (ps.t,
2
4
Phm), 131.8 (s, Php), 132.6 (ps.t, J C-P + J C-P ) 7.3 Hz, Pho),
139.7 (s, py-4), 159.0 (s, py-2,6).
2J C-P + 4J C-P ) 6.8 Hz, PPho), 134.1 (ps.t, J C-P + 4J C-P ) 6.8
2
Hz, PPho′), 140.4 (s, py-4), 145.8 (s, CPh), 159.6 (s, py-2,6). 31
P
[P t(P NP )(CH2CH(P h )OH)]BF 4 (18). Yield: 151 mg (0.173
1
1
mmol, 75%), white solid. H NMR (200 MHz, CD2Cl2): δ 1.47
NMR (162 MHz, CD2Cl2): δ 30.3 (s, J P-Pt ) 3110 Hz).
3
(d, J H-H ) 2.8 Hz, 1H, OH), 2.05-2.18 (m, 2H, CH2), 4.28-
Rea ction of 5 a n d 6 w ith CD3OD. A 6 mg sample of
complex 5 or 6 was dissolved in 0.5 mL of CD3OD, and ca. 2
equiv of NaHCO3 was added. After shaking the mixture in an
NMR tube for 5 min a 1H NMR spectrum was recorded.
[P t(P NP )(CH(Me)CH(Me)OCD3)]BF 4 (12a -d 3, fr om 5).
4.60 (m, 5H, CH, PCH2), 6.70 (m, 2H, CPh), 7.04 (m, 3H, CPh),
7.50-8.05 (m, 23H, PPh, py). 13C NMR (50 MHz, CD2Cl2/CD3-
NO2): δ 14.0 (s, PtCH2), 46.1 (m, PCH2), 78.9 (m, CH), 123.8
(br, py-3,5), 125.8 (s, CPh), 127.8 (s, CPh), 129.0 (s, CPh), 130.5
3
(ps.t, J C-P
+
5J C-P ) 5.7 Hz, PPhm), 133.3 (s, PPhp), 134.3
4
3
1H NMR (200 MHz, CD3OD): δ 0.78 (d, J H-H ) 6.0 Hz, 3H,
2
(ps.t, J C-P + J C-P ) 7.8 Hz, PPho), 141.1 (s, py-4), 146.4 (s,
3
3
CH3), 0.95 (d, J H-H ) 7.0 Hz, J H-Pt ) 58 Hz, 3H, CH3), 2.34
CPh), 160.5 (s, py-2,6). 31P NMR (162 MHz, CD2Cl2): δ 31.0
(m, 2J H-Pt ) 81 Hz, 1H, CH), 2.74 (m, 1H, CH) 4.58 (ps.t, 2J H-P
+ J H-P ) 4.7 Hz, 4H, PCH2), 7.55-8.02 (m, 23H, Ph, py).
1
(s, J P-Pt ) 3052 Hz).
4
[P t(P NP )(MeCN)](BF 4)2 (22). To a solution of 200 mg
(0.228 mmol) of the ethylene complex 1 in 6 mL of CH2Cl2 was
added ca. 20 equiv of MeCN. The mixture was stirred for 1 h
at room temperature. The product was precipitated by drop-
wise addition of diethyl ether. The white solid was filtered off,
washed two times with diethyl ether, and dried under vacuum.
[P t(P NP )(CH(Me)CH(Me)OCD3)]BF 4 (12b-d 3, fr om 6).
3
1H NMR (200 MHz, CD3OD): δ 0.96 (d, J H-H ) 6.2 Hz, 3H,
3
3
CH3), 1.06 (d, J H-H ) 6.9 Hz, J H-Pt ) 57 Hz, 3H, CH3), 2.19
2
(m, J H-Pt ) 85 Hz, 1H, CH), 2.56 (m, 1H, CH) 4.60 (m, 4H,
PCH2), 7.50-8.06 (m, 23H, Ph, py).
[P t(P NP )(CHdCHP h )]BF 4 (13). Complex 11 was dis-
solved in MeOH. After 2 h a pale yellow crystalline solid
precipitated, which was filtered off, washed with diethyl ether,
1
Yield: 198 mg (0.218 mmol, 95%). H NMR (200 MHz, CD2-
3
2
Cl2): δ 2.42 (s, J H-Pt ) 12 Hz, 3H, CH3), 4.64 (ps.t, J H-P
+
4J H-P ) 4.7 Hz, 4H, PCH2), 7.60-7.97 (m, 22H, Ph, py), 8.17
(t, J H-H ) 8.0 Hz, 1H, py).
1
and dried under vaccum. H NMR (200 MHz, CD2Cl2): δ 4.55
3
(ps.t, 2J H-P + 4J H-P ) 4.8 Hz, 4H, PCH2), 6.12 (d, 1H, 3J H-H
)
16.6 Hz, 2J H-Pt ) 78 Hz, CH), 6.84 (m, 2H, CPh), 7.09 (m, 2H,
[P t(P NP )(P h NH2)](BF 4)2 (21). To a solution of 150 mg
(0.165 mmol) of the acetonitrile complex 22 in 4 mL of CH2Cl2
was added ca. 10 equiv of PhNH2. The mixture was stirred
for 1 h at room temperature. The product was precipitated by
dropwise addition of diethyl ether. The white solid was filtered
off, washed three times with diethyl ether, and dried under
vacuum. Yield: 141 mg (0.146 mmol, 89%). 1H NMR (200 MHz,
CD2Cl2): δ 4.64 (ps.t, 2J H-P + 4J H-P ) 4.7 Hz, 4H, PCH2), 6.39
3
CPh), 7.56-7.84 (m, 23H, PPh, py), 7.84 (dt, 1H, J H-P ) 6.0
3
Hz, PtCH), 8.08 (t, J H-H ) 8.2 Hz). 13C NMR (50 MHz, CD2-
1
Cl2): δ 45.5 (ps.t, J C-P
+
3J C-P ) 16.3 Hz, PCH2), 118.9 (t,
3 5
3J C-P ) 9.1 Hz, CH), 123.6 (ps.t, J C-P + J C-P ) 5.1 Hz, py-
1
3
3,5), 125.3 (s, Ph), 126.2 (s, Ph), 127.4 (ps.t, J C-P + J C-P
)
29.1 Hz, PPhi), 129.9 (ps.t, 3J C-P + 5J C-P ) 5.4 Hz, Phm), 132.7
2
4
(s, PPhp), 133.6 (ps.t, J C-P + J C-P ) 7.3 Hz, PPho), 139.2 (t,
4J C-P ) 5.5 Hz, CH), 140.8 (s, py-4), 160.5 (s, py-2,6).
3
3
(br, J H-Pt ) 68 Hz, 2H, NH2), 6.40 (d, J H-H ) 7.8 Hz, 2H,