2778 Organometallics, Vol. 24, No. 11, 2005
Amijs et al.
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) 1.664 g/cm3, µ(Mo KR) ) 5.787 mm-1, crystal size 0.10 ×
0.15 × 0.45 mm, colorless; 11 874 reflections measured (θmax
) 27.5°), 5565 unique reflections, Rint ) 0.044, 4326 reflections
with I > 2σ(I). R ) 0.0303, wR2 ) 0.0591, S ) 0.99, -0.85 <
∆F < 1.05 e/Å3.
Crystal data for 13: C25H33N3Pd‚0.5(C6H6), triclinic, space-
group P1h(#2), a ) 9.199(2) Å, b ) 11.3015(10) Å, c ) 12.6747-
(10) Å, R ) 101.723(7)°, â ) 99.966(12)°, γ ) 101.409(13)°, V
) 1233.1(3) Å3, Z ) 2, dx ) 1.403 g/cm3, µ(Mo KR) ) 0.773
mm-1, crystal size 0.05 × 0.10 × 0.62 mm, yellowish; 7096
reflections measured, 5620 unique, Rint ) 0.06.4331 reflections
with I > 2σ(I). R ) 0.0532, wR2 ) 0.1227, S ) 1.05, -0.89 <
∆F < 1.19 e/Å3.
General Procedure for the Synthesis of NCN-Pt-aryl
Complexes 6-9. A solution of the aryl/naphthyllithium
compound (1.5 mmol) in Et2O (30 mL) was added dropwise to
a white suspension of [PtCl(NCN)] 1 (1.2 mmol, 0.8 equiv) in
Et2O (20 mL) at -78 °C over a period of 30 min. The resulting
suspension was allowed to warm to room temperature, where-
upon the color changed to pale yellow. The reaction mixture
was stirred for 4 h, and then all volatiles were removed in
vacuo. The solid residue was dissolved in CH2Cl2 (50 mL) and
filtered through a short path of Celite. The solvent was
removed under reduced pressure and the product thoroughly
washed with acetone (15 mL) and pentane (15 mL) to yield
an (off-)white powder.
1H, ArH (η1-C)), 8.15 (d, JH,H ) 8 Hz, 1H, ArH (η1-C)), 9.89
(d, 3JH,H ) 8 Hz, 1H, ArH-8 (η1-C)). 13C{1H} NMR (75.5 MHz):
δ 46.3 (NMe2 (η1-C)), 55.1 (NMe2 (η3-NCN)), 55.5 (NMe2 (η3-
NCN)), 68.6 (CH2N (η1-C)), 81.3 (CH2N (η3-NCN)), 119.4 (ArC-
3,5 (η3-NCN)) 122.7, 122.9, 123.3, 124.1, 129.3, 134.7, 135.4,
143.9, 145.6, 146.1, 172.8 (ArCipso (η3-NCN)), 183.6 (ArCipso (η1-
C)). Anal. Calcd for C25H33N3Pt: C, 52.62; H, 5.83; N, 7.36.
Found: C, 52.47; H, 5.72; N, 7.31.
[Pt(NCN)(C6H4(CH2NMe2)-2)] (9). Yield: 0.53 g (1.01
mmol, 85%). Mp: 209 °C (dec). 1H NMR (300 MHz): δ 2.43 (s,
6H, NMe2 (η1-C)), 2.49 (s, 3JH,Pt ) 44 Hz, 6H, NMe2 (η3-NCN)),
2.54 (s, JH,Pt ) 44 Hz, 6H, NMe2 (η3-NCN)), 3.43/3.61 (AB,
3
2JH,H ) 14 Hz, JH,Pt ) 45 Hz, 4H, CH2N (η3-NCN)), 4.25 (s,
3
2H, JH,Pt ) 126 Hz, CH2N (η1-C)), 6.91 (d, JH,H ) 7 Hz, 2H,
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3
ArH-3,5 (η3-NCN)), 7.17 (t, 3JH,H ) 8 Hz, 1H, ArH-4 (η3-NCN)),
7.34 (t, JH,H ) 7 Hz, 1H, ArH (η1-C)), 7.48 (t, JH,H ) 6 Hz,
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1H, ArH (η1-C)), 7.85 (d, 3JH,H ) 7 Hz, 1H, ArH-3 (η1-C)), 8.07
(d, JH,H ) 6 Hz, JH,Pt ) 33 Hz, 1H, ArH-6 (η1-C)). 13C{1H}
NMR (75.5 MHz): δ ) 46.0 (NMe2 (η1-C)), 54.5 (NMe2
(η3-NCN)), 54.7 (NMe2 (η3-NCN)), 69.1 (2JC,Pt ) 34 Hz, CH2N
(η1-C)), 81.0 (3JC,Pt ) 34 Hz, CH2N (η3-NCN)), 118.8 (ArC-3,5
(η3-NCN)), 122.2, 122.8, 125.8 (2JC,Pt ) 34 Hz), 139.5, 145.5
(2JC,Pt ) 50 Hz), 147.1, 173.0 (1JC,Pt ) 591 Hz, ArCipso (η3-NCN)),
183.8 (1JC,Pt ) 790 Hz, ArCipso (η1-C)). Anal. Calcd for C21H31N3-
Pt: C, 48.45; H, 6.00; N, 8.07. Found: C, 48.36; H, 5.94; N,
7.96.
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[Pd(NCN)(C10H6(CH2NMe2)-2)] (13). To a suspension of
[PdBr{C10H6(CH2NMe2)-2}]2 (12) (0.57 g, 1.54 mmol) in THF
(30 mL) was added dropwise a solution of [Li(NCN)]2 (11) (0.41
g, 2.07 mmol, 1.3 equiv) in THF (20 mL) at -78 °C. The yellow
solution was allowed to warm to room temperature and stirred
for 1 h, after which time all volatiles were evaporated in vacuo.
The solid residue was dissolved in toluene (30 mL) and filtered
through a path of Celite. After removal of the solvent in vacuo
and subsequent washing with Et2O (5 × 10 mL), 13 was
isolated as an off-white powder (0.41 g, 0.84 mmol, 55%).
Needle-shaped crystals suitable for an X-ray crystal structure
determination were obtained by slow diffusion of pentane into
a benzene solution of 13. Mp: 149 °C (dec). 1H NMR (300
MHz): δ 2.30 (s, 6H, NMe2 (η1-C)), 2.47 (s, 12H, NMe2 (η3-
[Pt(NCN)(C10H7)] (6). Yield: 0.52 g (1.01 mmol, 91%).
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Mp: 213 °C (dec). H NMR (300 MHz): δ 2.37 (s, JH,Pt ) 44
3
Hz, 6H, NMe2), 2.42 (s, JH,Pt ) 44 Hz, 6H, NMe2), 3.50/3.55
2
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(AB, JH,H ) 14 Hz, JH,Pt ) 45 Hz, 4H, CH2N), 6.91 (d, JH,H
) 7 Hz, 2H, ArH-3,5 (η3-NCN)), 7.19 (t, JH,H ) 8 Hz, 1H,
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ArH-4 (η3-NCN)), 7.49 (t, JH,H ) 7 Hz, 1H, ArH (η1-C)), 7.67
3
(t, JH,H ) 7 Hz, 1H, ArH (η1-C)), 7.71 (t, JH,H ) 7 Hz, 1H,
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ArH (η1-C)), 7.80 (d, JH,H ) 8 Hz, 1H, ArH (η1-C)), 8.03 (d,
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3JH,H ) 8 Hz, 1H, ArH (η1-C)), 8.17 (d, JH,H ) 8 Hz, JH,Pt
unresolved, 1H, ArH (η1-C)), 9.53 (d, 3JH,H ) 8 Hz, 1H, ArH-8
(η1-C)). 13C{1H} NMR (75.5 MHz): δ 54.4 (NMe2), 55.2 (NMe2),
81.0 (ArCH2), 118.8 (ArC-3,5 (η3-NCN)), 121.8, 122.7, 123.0,
124.2, 126.5, 129.1, 135.0, 135.7, 136.0, 145.2, 145.6, 172.6
(ArCipso (η3-NCN)), 187.5 (ArCipso (η1-C)). Anal. Calcd for
C22H26N2Pt: C, 51.45; H, 5.10; N, 5.45. Found: C, 51.34; H,
5.08; N, 5.38.
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NCN)), 3.50/3.51 (AA′, JH,H ) 15 Hz, 4H, CH2N (η3-NCN)),
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4.46 (s, 2H, CH2N (η1-C)), 6.80 (d, JH,H ) 8 Hz, 2H, ArH-3,5
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(η3-NCN)), 7.09 (t, JH,H ) 7 Hz, 1H, ArH-4 (η3-NCN)), 7.47
[Pt(NCN)(C10H5(Me)-2)] (7). Yield: 0.45 g (0.85 mmol,
(dt, 3JH,H ) 7 Hz, 4JH,H ) 1 Hz, 1H, ArH (η1-C)), 7.64 (dt, 3JH,H
71%). Mp: 189 °C (dec). 1H NMR (300 MHz): δ 2.37 (s, 3JH,Pt
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) 7 Hz, JH,H ) 1 Hz, 1H, ArH (η1-C)), 7.81 (d, JH,H ) 8 Hz,
) 43 Hz, 6H, NMe2), 2.40 (s, JH,Pt ) 43 Hz, 6H, NMe2), 3.23
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1H, ArH (η1-C)), 7.96 (d, JH,H ) 8 Hz, 1H, ArH (η1-C)), 8.06
(s, JH,Pt ) 8 Hz, 3H, ArMe), 3.53 (AA′, JH,Pt ) 44 Hz, 4H,
3
(d, 3JH,H ) 8 Hz, 1H, ArH (η1-C)), 9.65 (dd, 3JH,H ) 8 Hz, 4JH,H
) 1 Hz, 1H, ArH-8 (η1-C)). 13C{1H} NMR (75.5 MHz): δ 46.4
(NMe2 (η1-C)), 53.9 (NMe2 (η3-NCN)), 69.8 (CH2N (η1-C)), 78.4
(CH2N (η3-NCN)), 119.6 (ArC-3,5 (η3-NCN)) 123.3, 123.5, 124.0,
124.4, 127.1, 129.4, 134.6, 135.2, 143.8, 144.9, 146.2, 174.2
(ArCipso (η3-NCN)), 183.4 (ArCipso (η1-C)). Anal. Calcd for
C25H33N3Pd: C, 62.30; H, 6.90; N, 8.72. Found: C, 62.18; H,
6.86; N, 8.64.
CH2N), 6.91 (d, JH,H ) 7 Hz, 2H, ArH-3,5 (η3-NCN)), 7.19 (t,
3JH,H ) 7 Hz, 1H, ArH-4 (η3-NCN)), 7.44 (t, 3JH,H ) 7 Hz, 1H,
ArH-6,7 (η1-C)), 7.61 (d, 3JH,H ) 8 Hz, 1H, ArH (η1-C)), 7.66 (t,
3JH,H ) 8 Hz, 1H, ArH-6,7 (η1-C)), 7.80 (d, JH,H ) 8 Hz, 1H,
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ArH (η1-C)), 8.00 (d, JH,H ) 8 Hz, 1H, ArH (η1-C)), 9.73 (d,
3
3JH,H ) 8 Hz, 1H, ArH-8 (η1-C)). 13C{1H} NMR (75.5 MHz): δ
25.8 (3JC,Pt ) 32 Hz, ArMe), 54.7 (NMe2), 55.1 (NMe2), 81.0
(3JC,Pt ) 28 Hz, CH2N), 118.7, 122.5, 122.6, 123.3, 128.9, 129.1,
133.9, 134.3, 140.9, 145.2 (2JC,Pt ) 43 Hz), 172.7 (1JC,Pt ) 598
Hz, Cipso (η3-NCN)), 181.5 (1JC,Pt ) 826 Hz, Cipso (η1-C)). Anal.
Calcd for C23H28N2Pt: C, 52.36; H, 5.35; N, 5.31. Found: C,
52.43; H, 5.41; N, 5.03.
Reaction of 8 and 9 with HCl. Method A. Through a
solution of 8 (0.07 g, 0.12 mmol) or 9 (0.07 g, 0.13 mmol) in
CH2Cl2 (10 mL) was bubbled dry gaseous HCl for 5 min. The
solutions were evaporated in vacuo, after which pentane (5
mL) was added. Removal of the solvent yielded white powders.
1H NMR analysis in C6D6 showed for both complexes only the
presence of 1. Method B. To a solution of 8 (23 mg, 0.04 mmol)
or 9 (21 mg, 0.04 mmol) in CH2Cl2/MeOH (5 and 0.5 mL,
respectively) was added a solution of [SnMeCl3] (9 mg, 0.4
mmol) in CH2Cl2 (2 mL). After being stirred for 1.5 h, the
solutions were concentrated in vacuo. 1H NMR analysis in
CDCl3 showed the presence of 1 and [C10H7(CH2NMe2)-2] or
[C6H5(CH2NMe2)] for 8 or 9, respectively.
[Pt(NCN)(C10H6(CH2NMe2)-2)] (8). Yield: 0.40 g (0.70
mmol, 65%). Crystallization by slow diffusion of pentane into
a benzene solution of 8 afforded needle-shaped crystals suit-
able for single-crystal X-ray structure determination. Mp: 160
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°C (dec). H NMR (300 MHz): δ 2.36 (s, JH,Pt ) 41 Hz, 6H,
NMe2 (η3-NCN)), 2.47 (s, 6H, NMe2 (η1-C)), 2,49 (s, 3JH,Pt ) 41
Hz, 6H, NMe2 (η3-NCN)), 3.47/3.51 (AB, JH,H ) 14 Hz, JH,Pt
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) 45 Hz, 4H, CH2N (η3-NCN)), 4.50 (s, 2H, JH,Pt ) 39 Hz,
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CH2N (η1-C)), 6.92 (d, JH,H ) 7 Hz, 2H, ArH-3,5 (η3-NCN)),
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7.19 (t, JH,H ) 8 Hz, 1H, ArH-4 (η3-NCN)), 7.46 (t, JH,H ) 7
Reaction of 8 with I2. To a solution of 8 (9 mg, 16 µmol)
in CD2Cl2 (0.5 mL) was added a solution of I2 in CD2Cl2 (0.1
mL, 0.16 M, 1 equiv). Immediately, a bright red colored
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Hz, 1H, ArH (η1-C)), 7.65 (t, JH,H ) 7 Hz, 1H, ArH (η1-C)),
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7.86 (d, JH,H ) 8 Hz, 1H, ArH (η1-C)), 8.00 (d, JH,H ) 8 Hz,
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