Trans-cyclometalated Platinum(II) Complexes
Organometallics, Vol. 20, No. 12, 2001 2479
added to the hot filtrate. The precipitate was collected and
purified by column chromatography (neutral alumina, CH2-
Cl2 as eluent) to give golden yellow crystals (0.41 g, 83%).
[P t(C∧N∧C)tBu p y] (1). A mixture of [Pt(C∧N∧C)dmso] (0.05
g, 0.10 mmol) and excess 4-tert-butylpyridine (25 µL, 0.17
mmol) in chloroform (10 mL) was stirred for 12 h under N2
atmosphere at room temperature. The resulting solution was
evaporated to dryness, then purified by column chromatogra-
phy (neutral alumina, CH2Cl2 as eluent) to give golden yellow
crystals (0.05 g, 96%). Anal. Calcd for C26H24N2Pt: C, 55.81;
H, 4.32; N, 5.01. Found: C, 55.80; H, 4.33; N, 4.63. FAB-MS:
m/z 560 [M+ + H]. 1H NMR (CD2Cl2): 8.96 (d with 195Pt
166.1, 151.1, 139.5, 139.1, 129.6, 124.0, 123.2, 114.7, 33.7 (d,
J PC ) 29.6 Hz), 30.2, 27.7 (d, J PC ) 10.9 Hz), 26.5. 31P{1H}
NMR (CDCl3): 23.8 (1J PtP ) 3803 Hz).
[P t 2(C∧N∧C)2(µ-d cp m )] (6). The procedure for
1 was
adopted using 2 molar equiv of [Pt(C∧N∧C)dmso] and 1 equiv
of bis(dicyclohexylphosphino)methane. Yield: 0.06 g, 99%.
Anal. Calcd for 6‚H2O, C59H70N2OP2Pt2: C, 55.57; H, 5.53; N,
2.20. Found: C, 55.88; H, 5.46; N, 1.98. FAB-MS: m/z 1258
1
[M+ + H]. H NMR (CDCl3): 7.69 (d with 195Pt satellites, 4H,
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3
3J ) 7.2 Hz, J PtH ) 19.5 Hz), 7.61 (t, 2H, J ) 7.8 Hz), 7.46
3
3
3
(d, 4H, J ) 7.3 Hz), 7.31 (d, 4H, J ) 7.8 Hz), 7.11 (t, 4H, J
) 7.2 Hz), 7.06 (t, 4H, 3J ) 7.2 Hz), 3.49 (t with 195Pt satellites,
3
3
3
2
3
satellites, 2H, J ) 6.8 Hz, J PtH ) 43.6 Hz), 7.50 (t, 1H, J )
2H, J PH ) 11.7 Hz, J PtH ) 24.8 Hz), 2.80 (m, 4H), 2.56 (br s,
4H), 2.32 (br t, 4H), 1.75-1.30 (m, 20H), 1.48 (m, 4H), 1.00
(m, 8H). 13C{1H} NMR (CDCl3): 166.1, 166.0, 150.7, 139.6,
139.4, 129.6, 123.8, 123.4, 114.5, 37.2 (br), 31.3, 31.1, 27.6, 26.5.
31P{1H} NMR (CDCl3): 12.0 (1J PtP ) 3828 Hz).
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3
7.8 Hz), 7.48 (d, 2H, J ) 7.2 Hz), 7.43 (d, 2H, J ) 7.8 Hz),
7.27 (d, 2H, 3J ) 7.1 Hz), 7.23 (t, 2H, 3J ) 7.8 Hz), 7.08 (t, 2H,
3J ) 7.8 Hz), 6.99 (d with 195Pt satellites, 2H, 3J ) 7.8 Hz,
4J PtH ) 24.2 Hz), 1,44 (s, 9H, CMe3). 13C{1H} NMR (CDCl3):
171.9, 168.1, 160.9, 153.1, 149.4, 139.3, 133.2, 130.4, 123.9,
123.6, 123.3, 114.2, 35.2 (CMe3), 30.3 (CMe3).
[P t(C∧N∧C)P P h 3] (7). The procedure for 1 was adopted
using excess triphenylphosphine. Yield: 0.07 g, 98%. Anal.
Calcd for C35H26NPPt: C, 61.22; H, 3.82; N, 2.04. Found: C,
61.26; H, 3.74; N, 1.79. FAB-MS: m/z 687 [M+ + H]. 1H NMR
(CDCl3): 7.90 (m, 6H), 7.66 (t, 1H, 3J ) 7.9 Hz,), 7.50-7.32
(m, 13H), 6.94 (t, 2H, 3J ) 7.4 Hz), 6.70 (t with 195Pt satellites,
[P t(C∧N∧C)MQ]P F 6 (2(P F 6)). A mixture of [Pt(C∧N∧C)-
dmso] (0.05 g, 0.10 mmol) and 1-methyl-4,4′-bipyridinium
(MQ+) hexafluorophosphate (0.03 g, 0.10 mmol) in dichlo-
romethane/acetone (5:5 mL) was stirred under N2 atmosphere
at room temperature for 48 h. The resultant suspension was
evaporated to dryness. The crude solid was washed with
acetone then dichloromethane and twice recrystallized from
acetone/ether to give orange needles (0.06 g, 80%). Anal. Calcd
for C28H22N3PtPF6: C, 45.41; H, 2.99; N, 5.67. Found: C, 45.37;
H, 2.98; N, 5.67. FAB-MS: m/z 596 [M+ + H]. 1H NMR
(acetone-d6): 9.37 (d, 2H, 3J ) 6.8 Hz), 9.32 (d with 195Pt
3
4
2H, J ) 7.4 Hz, J PtH ) 7.3 Hz), 6.27 (d with 195Pt satellites,
2H, 3J ) 7.5 Hz, J PtH ) 26.1 Hz). 13C{1H} NMR (CDCl3):
3
166.6, 165.6 (d, J PC ) 7.0 Hz), 150.9, 140.3, 138.8, 135.5 (d,
J PC ) 11.6 Hz), 132.2 (d, J PC ) 57.3 Hz), 130.4, 129.6, 128.1
(d, J PC ) 10.8 Hz), 123.8, 123.5, 114.7. 31P{1H} NMR (CDCl3):
29.9 (1J PtP ) 4085 Hz).
[P t2(C∧N∧C)2(µ-d p p m )] (8). The procedure for 1 was
adopted using 2 molar equiv of [Pt(C∧N∧C)dmso] and 1 equiv
of bis(diphenylphosphino)methane. Yield: 0.06 g, 97%. Anal.
Calcd for C59H44N2P2Pt2: C, 57.47; H, 3.60; N, 2.27. Found:
3
3
3
satellites, 2H, J ) 6.8 Hz, J PtH ) 44.9 Hz), 8.90 (d, 2H, J )
6.8 Hz), 8.30 (d, 2H, 3J ) 6.8 Hz), 7.75 (t, 1H, 3J ) 7.6 Hz),
7.58 (d, 2H, 3J ) 6.8 Hz), 7.51 (d with 195Pt satellites, 3J ) 7.6
4
3
3
1
C, 57.90; H, 3.87; N, 2.16. FAB-MS: m/z 1234 [M+ + H]. H
Hz, J PtH ) 10.3 Hz), 7.12 (t, 2H, J ) 6.9 Hz), 7.02 (t, 2H, J
) 7.4 Hz), 6.87 (d with 195Pt satellites, 2H, J ) 7.0 Hz, J PtH
) 24.8 Hz), 4.75 (s, 3H, Me). 13C{1H} NMR (DMSO-d6): 166.0,
165.7, 151.5, 150.6, 149.1, 145.8, 142.0, 140.5, 136.0, 130.0,
124.6, 124.3, 124.2, 121.5, 115.3, 47.3 (Me).
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3
NMR (CDCl3): 7.83 (m, 8H), 7.63 (t, 2H, J ) 7.9 Hz), 7.35-
7.20 (m, 8H), 7.22-7.18 (m, 12H), 6.89 (t, 4H, 3J ) 7.4 Hz),
6.74 (t, 4H, 3J ) 7.3 Hz), 6.54 (d with 195Pt satellites, 4H, 3J )
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2
7.4 Hz, J PtH ) 25.6 Hz), 4.67 (t with 195Pt satellites, 2H, J PH
[P t2(C∧N∧C)2(µ-p yr )] (3). A mixture of [Pt(C∧N∧C)dmso]
(0.05 g, 0.10 mmol) and pyrazine (4 mg, 0.05 mmol) in
dichloromethane (10 mL) was stirred under N2 atmosphere
at room temperature for 48 h. The resultant deep red suspen-
sion was collected, washed with dichloromethane, and twice
recrystallized from boiling chloroform to give deep red needles
(0.04 g, 75%). Anal. Calcd for 3‚CHCl3, C39H27N4Cl3Pt2: C,
44.69; H, 2.60; N, 5.35. Found: C, 44.84; H, 2.58; N, 5.54. FAB-
MS: m/z 929 [M+ + H]. 1H NMR (DMSO-d6): 8.65 (s, 4H,
pyrazine), 7.83 (t, 2H, 3J ) 8.1 Hz), 7.76 (d with 195Pt satellites,
4H, 3J ) 7.4 Hz, 3J PtH ) 15.4 Hz), 7.64 (m, 8H), 7.19 (t, 4H, 3J
) 7.3 Hz), 7.07 (t, 4H, 3J ) 7.4 Hz). 13C{1H} NMR (DMSO-d6):
166.1, 165.8, 149.2, 145.0, 142.1, 136.1, 130.1, 124.4, 124.3.
115.4.
) 12.3 Hz, J PtH ) 26.5 Hz). 13C{1H} NMR (CDCl3): 167.1 (d,
3
J PC ) 7.3 Hz), 165.8, 150.5, 139.2, 138.3, 134.3 (d, J PC ) 12.9
Hz), 130.7 (d, J PC ) 55.3 Hz), 130.0, 129.0, 127.4 (d, J PC
)
11.1 Hz), 123.6, 122.8, 114.3, 27.5 (PCH2P). 31P{1H} NMR
(CDCl3): 15.7 (1J PtP ) 4147 Hz).
[P t3(C∧N∧C)3(µ3-d p m p )] (9). The procedure for 1 was
adopted using 3 molar equiv of [Pt(C∧N∧C)dmso] and 1 equiv
of bis(diphenylphosphinomethyl)phenylphosphine. Yield: 0.05
g, 93%. Anal. Calcd for C83H62N3P3Pt3: C, 56.02; H, 3.51; N,
2.36. Found: C, 55.80; H, 3.61; N, 2.19. FAB-MS: m/z 1780
[M+ + H]. 1H NMR (CD2Cl2): 7.77-7.65 (m, 8H), 7.53-7.46
(m, 7H), 7.25 (d, 4H, 3J ) 7.3 Hz), 7.18 (m, 4H), 7.12 (t, 2H, 3J
) 7.4 Hz), 7.08-6.97 (m, 8H), 6.90-6.80 (m, 7H), 6.79-6.76
3
(m, 6H), 6.35 (br, 4H), 6.17 (br, 4H), 5.62 (t, 2H, J ) 7.1 Hz),
[P t(C∧N∧C)CN(C6H3Me2-2,6)] (4). The procedure for 1 was
adopted using excess 2,6-dimethylphenylisocyanide. Yield:
0.05 g, 95%. Anal. Calcd for C26H20N2Pt: C, 56.21; H, 3.63; N,
5.04. Found: C, 55.89; H, 3.46; N, 4.69. FAB-MS: m/z 556 [M+
5.31 (m, 2H), 5.28 (t, 2H, J ) 7.7 Hz), 4.59 (m, 2H). 13C{1H}
3
NMR (CDCl3): 167.6 (d, J PC ) 8.0 Hz), 166.4, 165.9 (d, J PC
6.7 Hz), 165.7, 165.6 (d, J PC ) 6.3 Hz), 150.5, 150.3 (d, J PC
)
)
27.0 Hz), 141.3, 139.5, 138.4, 137.3, 136.2 (d, J PC ) 56.3 Hz),
134.5 (d, J PC ) 11.1 Hz), 133.9 (d, J PC ) 54.9 Hz), 132.4 (dd,
1J PC ) 47.2 Hz, 3J PC ) 11.2 Hz), 129.9 (d, J PC ) 52.3 Hz), 129.4,
1
+ H]. IR (Nujol): ν 2155 (CtN) cm-1. H NMR (CDCl3): 7.78
(d with 195Pt satellites, 2H, 3J ) 7.1 Hz, 3J PtH ) 25.6 Hz), 7.63
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3
(t, 1H, J ) 8.0 Hz), 7.49 (d, 2H, J ) 7.6 Hz), 7.35-7.18 (m,
129.1 (d, J PC ) 13.6 Hz), 127.5 (dd, J PC ) 47.4 Hz, J PC )
7H), 7.12 (t, 2H, J ) 7.5 Hz), 2.58 (s, 6H, Me). 13C{1H} NMR
11.0 Hz), 124.7, 123.4, 123.1, 122.8, 122.3 (d, J PC ) 51.0 Hz),
114.3, 113.8 (d, J PC ) 24.5 Hz), 22.7 (br t, PCH2P). 31P{1H}
NMR (CD2Cl2): 14.8 (1J PtP ) 4091 Hz), 11.7 (1J PtP ) 4232 Hz).
X-r a y Cr ysta llogr a p h y. Crystals of 1 (benzene; evapora-
tion), 3‚CHCl3 (chloroform), 4 and 7 (diethyl ether diffusion
into chloroform/benzene), and 6‚CHCl3‚CH3OH‚4H2O (chloro-
form/methanol; evaporation) were obtained. Crystals of 8
exhibited two forms with different colors; the yellow form was
obtained by slow diffusion of diethyl ether into chloroform/
benzene solution, while the orange form (8‚CHCl3) was grown
by slow evaporation of a chloroform/methanol solution. Crystal
data and details of data collection and refinement for 1, 4, 8
3
(CDCl3): 168.0, 167.7, 149.8, 140.9, 138.6, 134.6, 131.4, 128.4,
128.1, 124.4, 124.3, 115.1, 19.2 (Me).
[P t(C∧N∧C)P Cy3] (5). The procedure for 1 was adopted
using tricyclohexylphosphine. Yield: 0.07 g, 96%. Anal. Calcd
for C35H44NPPt: C, 59.65; H, 6.29; N, 1.99. Found: C, 59.31;
H, 6.18; N, 1.79. FAB-MS: m/z 706 [M+ + H]. 1H NMR
(CDCl3): 7.76 (d with 195Pt satellites, 2H, 3J ) 7.4 Hz, 3J PtH
)
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25.2 Hz), 7.60 (t, 1H, J ) 7.9 Hz), 7.46 (d, 2H, J ) 7.6 Hz),
7.31 (d, 2H, 3J ) 7.9 Hz), 7.15 (t, 2H, 3J ) 7.4 Hz), 7.04 (t, 2H,
3J ) 7.4 Hz), 2.66 (m, 3H), 2.14 (m, 6H), 1.76-1.67 (m, 15H),
1.21 (m, 9H). 13C{1H} NMR (CDCl3): 166.5 (d, J PC ) 7.0 Hz),