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9
compound as a white solid. Yield 3.29 g, 32%. 1H NMR (400 MHz,
4.1.4. Synthesis of trans-Pt(C„CAr)(C6H4NAr2)(PPh3)2 (4a)
CDCl3) d 7.16 (d, J = 7 Hz, 2H), 7.05 (d, J = 9 Hz, 4H), 6.94 (d,
J = 7 Hz, 2H), 6.90–6.85 (m, 1H), 6.82 (d, J = 9 Hz, 4H), 3.80 (s, 6H).
Literature:[47] 1H NMR (CDCl3): d = 7.25–6.79 (m, 13H, Ar),
3.79 ppm (s, 6H, OCH3). ESI-MS: 305.6 [M]+.
4.1.2. Synthesis of N(C6H4I-4)Ar2 (2) [73]
An oven dried Schlenk flask was charged with dry HNEt2 (10 cm3)
and the solvent degassed. To this solution, 4-ethynylanisole
(0.017 g, 0.13 mmol), 3 (150 mg, 0.13 mmol) and CuI (4 mg) were
added and the solution stirred at room temperature for 17 h. The
precipitate was filtered, washed with ethanol (3 ꢂ 5 cm3) and
methanol (3 ꢂ 5 cm3) and dried under airflow for 1 h. Yield
131 mg, 87%. 1H NMR (CD2Cl2): d 3.64 (s, 3H, Ht), 3.76 (s, 6H, Ha),
6.11 (d, J = 8 Hz, 2H, Hh), 6.15 (d, J = 9 Hz, 6H, Hr), 6.43 (d,
J = 9 Hz, 2H, Hq), 6.71 (d, J = 8 Hz, 2H, Hg), 6.73 (m, 8H, Hc and d)
7.32 (vt, J = 8 Hz, 12H, Hk), 7.40 (t, J = 8 Hz, 6H, Hm), 7.64 (m,
12H, Hl). 31P NMR (CD2Cl2): 20.84 (JPt-P = 2985 Hz). 13C NMR (CD2-
Cl2): 156.77 (Cs, s), 154.29 (Cb, s), 142.31 (Ce, s), 141.55 (Cf, s),
139.55 (Cg, s), 134.84 (Cl, t, JC-P = 5 Hz), 131.79 (Cj, t, JC-P = 28 Hz),
131.35 (Cq, s),129.75 (Cm, s), 127.58 (Ck, t, JC-P = 5 Hz), 124.10 (Cc,
s), 123.94 (Ch, s), 121.74 (Cp, s), 113.92 (Cd, s), 112.71 (Cr,s),
55.40 (Ca, s), 54.96 (Ct, s). MALDI-MS(+) m/z: 1155.3 [M+H]+. IR
An oven dried Schlenk flask was charged with chloroform (90 mL)
and the solvent degassed. To this solution, 1 (3.00 g, 9.8 mmol) and
NIS (2.430 g, 10.8 mmol) were added with the exclusion of light fol-
lowed by acetic acid (60 mL) and the mixture stirred at room tem-
perature for 30 h and quenched with aqueous sodium thiosulphate
(300 mg in 30 mL H2O) and extracted with CH2Cl2 (3 ꢂ 30 mL). The
organic layers were combined and dried over MgSO4, filtered and
the solvent removed in vacuo to give an off-white solid. Yield
3.14 g, 75%). 1H NMR (400 MHz, CDCl3) d 7.40 (d, J = 8 Hz, 2H),
7.02 (d, J = 8 Hz, 4H), 6.82 (d, J = 8 Hz, 4H), 6.67 (d, J = Hz, 2H),
3.79 (s, 6H). Literature: 1H NMR (250 MHz, CDCl3): d 7.40/6.67
(m, AA0, 2 H/m, BB0, 2H; I–C6H4), 7.03/6.82 (m, AA0 BB0, 8H;
H3CO–C6H4), 3.79 (s, 6H; MeO) ESI-MS: 431.5 [M]+.
(CH2Cl2) m
(C„C) 2107 cmꢀ1. Anal. Calc. for: C, 67.58; H, 4.80; N,
1.21. Found: C, 67.45; H, 4.74; N, 1.17%.
4.1.5. Synthesis of trans-Pt(C„CC6H4NAr2)(C6H4NAr2)(PPh3)2 (4b)
4.1.3. Synthesis of trans-PtI(C6H4NAr2)(PPh3)2 (3)
An oven dried Schlenk flask was charged with dry toluene (20 cm3)
and the solvent degassed. To this solution, Pt(PPh3)4 (1.00 g,
0.804 mmol) and 4-iodophenylene-p-dianisylamine (0.693 g,
1.60 mmol) were added and the mixture stirred for 16 h at reflux.
The mixture was cooled to ambient temperature and added to vig-
orously stirred hexane (150 cm3) and the off-white precipitate was
filtered and washed with hexane (2 x 10 mL). Yield 880 mg, 95%. 1H
NMR (CD2Cl2) d 3.76 (s, 6H, Ha), 5.98 (d, J = 8 Hz, 2H, Hh), 6.71 (m,
10H, Hc,d and g) 7.34 (vt, J = 8 Hz, 12H, Hk), 7.41 (t, J = 8 Hz, 6H,
Hm), 7.62 (m, 12H, Hl). 31P NMR (CD2Cl2): 20.67 (JPt-P = 3074 Hz).
13C NMR (CD2Cl2): 154.72 (Cb, s), 142.22 (Ce, s), 141.78 (Cf, s),
136.17 (Cg, s), 135.08 (Cl, t, JC-P = 5 Hz), 131.80 (Cj, t, JC-P = 28 Hz),
129.88 (Cm, s), 127.58 (Ck, t, JC-P = 5 Hz), 125.19 (Cc, s), 122.99
(Ch, s), 113.99 (Cd, s), 55.39 (Ca, s). MALDI-MS(+) m/z: 1151.1
[M+H]+. Anal. Calc. for: C, 58.44; H, 4.20; N, 1.22. Found: C, 58.60;
H, 4.04; N, 1.29%.
An oven dried Schlenk flask was charged with 4-ethynylenepheny-
lenedi-p-anisylamine (0.043 g, 0.13 mmol) in dry CH2Cl2 and the
solvent removed in vacuo. Dry HNEt2 (10 cm3) was added and the
solvent degassed. To this solution, PtI(C6H4N(C6H4OCH3-
4)2)(PPh3)2 (150 mg, 0.130 mmol) and CuI (4 mg) were added and
the solution stirred at room temperature for 2 h. The precipitate
was filtered, washed with methanol (3 ꢂ 5 cm3), ethanol
(3 ꢂ 5 cm3) and hexane (3 ꢂ 5 cm3) and dried under airflow for
1 h. Yield 109 mg, 63%. 1H NMR (CD2Cl2): d 3.76 (s, 12H, Ha and
x), 6.03 (d, J = 8 Hz, 2H, Hq), 6.11 (d, J = 8 Hz, 2H, Hh), 6.44 (d,
J = 8 Hz, 2H, Hr), 6.68 (d, J = 8 Hz, 2H, Hg), 6.73 (m, 8H, Hc and d),
6.76 (d, J = 8 Hz, 4H, Hv), 6.89 (d, J = 8 Hz, 4H, Hu), 7.32 (vt,
J = 8 Hz, 12H, Hk), 7.39 (t, J = 8 Hz, 6H, Hm), 7.64 (m, 12H, Hl). 31P
NMR (CD2Cl2): 20.95 (JPt-P = 2981 Hz). 13C NMR (CD2Cl2): 155.48
(Cw, s), 154.29 (Cb, s), 145.33 (Ct, s), 142.31 (Ce, s), 141.59 (Cf, s),
141.12 (Cs, s), 139.53 (Cg, s), 134.84 (Cl, t, JC-P = 5 Hz), 131.781 (Cj,