S.-O. Hauber, J. Woo Seo, M. Niemeyer
ARTICLE
+
MS (70eV, 430 K): m/z (%) 195.1 (38.4) [MesC6H4 ], 313.3 (100)
Experimental Section
[2,6-Mes2C6H3–H+], 341.2 (15.1) [2,6-Mes2C6H3N2+], 523.4 (10.3)
[(2,6-Mes2C6H3)(C6H4Mes)NH+], 831.3 (2.4) [M+].
General Remarks
All manipulations were performed by using standard Schlenk tech-
niques in an inert atmosphere of purified argon and solvents freshly
distilled from sodium wire or LiAlH4. The triazenes Dmp(Mph)N3H
or Dmp(Tph)N3H [5] were synthesized as described previously. NMR
spectra were recorded in C6D6 with Bruker AM200, AC250 or AM400
instruments and referenced to solvent resonances. IR spectra were ob-
tained in the range 4000–200 cm–1 with a Perkin–Elmer paragon 1000
PC (Nujol mulls) or a Nicolet 6700 FT-IR (reflection data) spectrome-
ter. Mass spectra were recorded with a Varian MAT711 or Finnegan
MAT95 instrument. Melting points were determined under argon at-
mosphere in sealed glass tubes. No elemental analysis data for com-
pounds 2a–4b could be obtained due to mercury contamination prob-
lems. Therefore, purity of these compounds was proven by combined
NMR and mass spectrometry experiments.
Iodo-{[[N'-2-(2',4',6'-trimethyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (4a):
The synthesis was accomplished in a similar manner to the preparation
of 2a with use of triazene (1a) (1.10 g, 2 mmol), n-BuLi in n-hexane
(0.80 mL, 2.5 m, 2 mmol) and HgI2 (0.91 g, 2 mmol). Yield: 1.12 g
(1.17 mmol, 58 %); Mp: 192–194 °C. 1H NMR (400.1 MHz): δ =
1.63 (s, 6 H, o-CH3, biphenyl), 2.11 (s, 12 H, o-CH3, terphenyl), 2.24
(s, 3 H, p-CH3, biphenyl), 2.26 (s, 6 H, p-CH3, terphenyl), 6.73 (s, 2
H, m-Mes, biphenyl), 6.88 (s, 4 H, m-Mes, terphenyl), 6.73–7.17 (m,
7 H, various aryl-H). 13C NMR (100.6 MHz): δ = 20.3 (o-CH3, bi-
phenyl), 21.0 (o-CH3, terphenyl), 21.3 (p-CH3, terphenyl), 21.5 (p-
CH3, biphenyl), 120.1, 123.8, 126.2, 128.2, 129.0, 129.2, 129.6, 130.3
(aromatic CH), 128.3, 133.6, 135.1, 135.8, 136.5, 136.8, 137.6, 138.8,
143.6, 143.9 (aromatic C). IR (Nujol): 1716 w, 1699 w, 1611 m, 1557
w, 1436 w, 1418 w, 1316 m br, 1205 m, 1169 m br, 1099 m, 1069 w,
1026 m br, 981 m, 846 s, 806 s, 789 m, 759 s, 734 m, 688 m, 651 s,
697 m, 572 w, 511 m, 496 m, 462 m, 438 m cm–1. EI-MS (70eV,
420 K): m/z (%) 195.1 (45.4) [MesC6H4+], 313.2 (100) [2,6-
Mes2C6H3–H+], 341.2 (16.2) [2,6-Mes2C6H3N2+], 523.3 (8.2) [(2,6-
Mes2C6H3)(C6H4Mes)NH+], 897.2 (2.7).
Preparation of the Triazenido Mercury Halides
Chloro-{[[N'-2-(2',4',6'-trimethyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (2a):
To a stirred solution of 1a (1.10 g, 2 mmol) in ethyl ether (20 mL),
which was cooled in an ice bath was added n-BuLi in n-hexane
(0.80 mL, 2.5 m, 2 mmol) and stirring was continued for 30 min at the
same temperature. HgCl2 (0.54 g, 2.00 mmol) was afterwards added in
one portion and the resulting mixture was stirred at ambient tempera-
ture for 4 h. The volatile materials were removed under reduced pres-
sure and the remaining solid was extracted with n-heptane (20 mL).
After separation of the precipitated lithium halide by centrifugation the
filtrate was concentrated to incipient crystallization. Cooling in a
–20 °C freezer afforded 2a as yellow crystals. Yield: 0.88 g
(1.12 mmol, 56 %); Mp: 165–167 °C. 1H NMR (250.1 MHz): δ =
1.60 (s, 6 H, o-CH3, biphenyl), 2.11 (s, 12 H, o-CH3, terphenyl), 2.24
(s, 3 H, p-CH3, biphenyl), 2.26 (s, 6 H, p-CH3, terphenyl), 6.76 (s, 2
H, m-Mes, biphenyl), 6.89 (s, 4 H, m-Mes, terphenyl), 6.71–7.11 (m,
7 H, various aryl-H). 13C NMR (62.9 MHz): δ = 20.2 (o-CH3, bi-
phenyl), 21.0 (o-CH3, terphenyl), 21.2 (p-CH3, terphenyl), 21.3 (p-
CH3, biphenyl), 120.2, 123.8, 126.4, 128.3, 128.7, 129.5, 129.8, 130.3
(aromatic CH), 128.8, 132.9, 135.1, 135.7, 136.6, 136.8, 137.5, 139.2,
143.5, 143.6 (aromatic C). IR (Nujol): 1716 w, 1699 w, 1611 m, 1557
w, 1436 w, 1418 w, 1316 m br, 1206 m, 1186 m, 1164 m br, 1098 m,
1030 m br, 982 m, 911 w, 847 s, 805 ms, 790 m, 761 s, 735 m, 691
m, 652 s, 597 s, 576 m, 514 s, 499 m, 463 m, 463 m, 443 m cm–1.
Chloro-{[[N'-2-(2',4',6'-triisopropyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (2b):
The synthesis was accomplished in a similar manner to the preparation
of 2a with use of triazene (1b) (1.27 g, 2.00 mmol), n-BuLi in n-
hexane (0.80 mL, 2.5 m, 2 mmol) and HgCl2 (0.59 g, 2.17 mmol).
1
Yield: 1.46 g (1.68 mmol, 84 %); Mp: 173–175 °C (dec.). H NMR
3
(400.1 MHz): δ = 0.87, 0.90 (2 × d, JHH = 6.7 Hz, 2 × 6 H, o-
3
CH(CH3)2), 1.32 (d, JHH = 6.7 Hz, 6 H, p-CH(CH3)2), 2.11 (s, 12 H,
3
o-CH3), 2.24 (s, 6 H, p-CH3), 2.47 (sep, JHH = 6.7 Hz, 2 H, o-
3
CH(CH3)2), 2.86 (sep, JHH = 6.7 Hz, 1 H, p-CH(CH3)2), 6.69 (d,
3
3JHH = 8.2 Hz, 1 H, 6-C6H4), 6.85 (t, JHH = 7.7 Hz, 1 H, 4-C6H4),
6.88 (d, 1 H, 3-C6H4), 6.90 (s, 4 H, m-Mes), 7.00 (m, 2 H, m-C6H3),
7.06 (m, 1 H, p-C6H3), 7.12 (t, 1 H, 5-C6H4), 7.14 (s, 2 H, m-Trip).
13C NMR (100.6 MHz): δ = 21.0 (o-CH3), 21.2 (p-CH3), 24.1, 24.2
(o-CH(CH3)2), 24.7 (p-CH(CH3)2), 30.5 (o-CH(CH3)2), 34.8 (p-
CH(CH3)2), 119.3 (6-C6H4), 122.9 (4-C6H4), 123.0 (m-Trip), 126.6 (p-
C6H3), 128.6 (5-C6H4), 128.8 (m-Mes), 129.8 (m-C6H3), 131.2 (3-
C6H4), 127.0, 131.3, 135.2, 135.4, 136.5, 137.7, 143.4, 144.2, 147.6,
151.1 (aromatic C).
+
Iodo-{[[N'-2-(2',4',6'-triisopropyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (4b):
The synthesis was accomplished in a similar manner to the preparation
of 2a with use of triazene (1b) (0.83 g, 1.30 mmol), 0.52 mL of a
EI-MS (70eV, 430 K): m/z (%) 195.0 (32.6) [MesC6H4 ], 313.2 (100)
[2,6-Mes2C6H3–H+], 341.2 (12.4) [2,6-Mes2C6H3N2+], 523.3 (3.1)
[(2,6-Mes2C6H3)(C6H4Mes)NH+], 787.3 (2.7) [M+].
Bromo-{[[N'-2-(2',4',6'-trimethyl)biphenyl]-(N'''-2,4,6,2'',4'',6''- 2.5 m n-BuLi solution in n-hexane (0.52 mL, 2.5 m, 1.3 mmol) and
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (3a): HgI2 (0.70 g, 1.54 mmol). Yield: 1.14 g (1.18 mmol, 90 %); Mp:
1
3
The synthesis was accomplished in a similar manner to the preparation 152 °C (dec.). H NMR (250.1 MHz): δ = 0.91, 0.92 (2 × d, JHH
=
3
of 2a with use of triazene (1a) (1.10 g, 2 mmol), n-BuLi in n-hexane 6.8 Hz, 2 × 6 H, o-CH(CH3)2), 1.31 (d, JHH = 6.8 Hz, 6 H, p-
(0.80 mL, 2.5 m, 2 mmol) and HgBr2 (0.72 g, 2 mmol). Yield: 0.98 g CH(CH3)2), 2.21 (s, 12 H, o-CH3), 2.22 (s, 6 H, p-CH3), 2.51 (sep,
(1.18 mmol, 59 %); Mp: 161–163 °C. 1H NMR (200.1 MHz): δ = 3JHH = 6.8 Hz, 2 H, o-CH(CH3)2), 2.88 (sep, JHH = 6.8 Hz, 1 H, p-
3
1.61 (s, 6 H, o-CH3, biphenyl), 2.11 (s, 12 H, o-CH3, terphenyl), 2.24 CH(CH3)2), 6.97–7.01 (m, 7 H, various aryl-H), 6.89 (s, 4 H, m-Mes),
(s, 3 H, p-CH3, biphenyl), 2.26 (s, 6 H, p-CH3, terphenyl), 6.75 (s, 2 7.11 (s, 2 H, m-Trip). 13C NMR (62.9 MHz): δ = 21.1 (o-CH3), 21.2
H, m-Mes, biphenyl), 6.89 (s, 4 H, m-Mes, terphenyl), 6.70–7.19 (m, (p-CH3), 24.2, 24.5, 24.7 (o/p-CH(CH3)2), 30.6 (o-CH(CH3)2), 34.5
7 H, various aryl-H). 13C NMR (50.3 MHz): δ = 20.2 (o-CH3, bi- (p-CH(CH3)2), 119.0, 121.8, 122.9, 123.4, 126.3, 128.3, 130.0, 131.4
phenyl), 21.0 (o-CH3, terphenyl), 21.2 (p-CH3, terphenyl), 21.3 (p- (aromatic C-H), 129.7, 134.7, 135.5, 136.4, 137.9, 143.6, 144.6, 147.5,
CH3, biphenyl), 120.2, 123.8, 126.4, 128.3, 128.8, 129.5, 130.0, 130.3, 150.7 (aromatic C); one aromatic C signal could not be observed. IR
(aromatic CH), 129.0, 133.1, 135.1, 135.1, 136.6, 136.8, 137.5, 139.0, (Nujol) 1612 s, 1592 ms, 1568 s, 1313 vs, 1288 s, 1207 s, 1189 s,
143.6 (aromatic C); one aromatic C signal could not be observed. EI- 1166 vs. br, 1092 s, 1069 ms, 1054 ms, 1003 m, 978 m, 946 w, 937
754
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 750–757