Homoleptic Organometallic Compounds of Zinc, Cadmium, and Mercury
FULL PAPER
Bis[2,6-bis(dimethylaminomethyl)phenyl]mercury (2c): In a simi-
lar way to 2a, HgCl2 (0.25 g, 0.93 mmol) and 2 (0.37 g, 1.87 mmol) 0.32 (t, J ϭ 7.1 Hz, ZnCH2), 1.85 (quint, J ϭ 6.9/6.6 Hz, CH2),
crystals of 4a, m.p. 71°C. Ϫ 1H NMR (C6D6, T ϭ 338 K): δ ϭ
3
3
3
yielded 0.31 g (57%) of colorless fine crystalline 2c, m.p. 139°C.
The mixture was protected from light; although during the reac-
tion, the formation of mercury metal was observed. Ϫ 1H NMR
([D8]THF): δ ϭ 2.19 (s, CH3), 3.41 (CH2), 7.02-7.18 (m, CarylH).
1.86 (s, CH3), 2.23 (t, J ϭ 6.4 Hz, CH2N). Ϫ 13C NMR (C6D6):
δ ϭ 8.46 (ZnCH2), 25.87 (CH2), 41.87 (CH3), 61.17 (CH2N). Ϫ
MS; m/z (%): 177 (6) [1/2 M(64Zn)ϩ], 149 (13) [1/2 Mϩ Ϫ CH2CH2],
84 (100) [C5H10Nϩ], and others. Ϫ C14H30N2Zn2 (357.19): calcd.
C 47.08, H 8.47, N 7.84; found C 46.93, H 8.42, N 7.89.
Ϫ
13C NMR ([D8]THF):
δ ϭ 48.25 (CH3), 71.58 [sat.,
3J(13C,199Hg) ϭ 40.5 Hz, CH2], 129.20 (C-3,5), 130.60 (C-4), 150.80
(sat., C-2,6), 176.00 (sat., C-1). Ϫ MS; m/z (%): 584 (<1)
[M(202Hg)ϩ], 202 (1) [Hgϩ], and others as for 2a. Ϫ C24H38HgN4
(583.19): calcd. C 49.43, H 6.57, N 9.61; found C 49.21, H 6.33,
N 9.48.
(5,13-Diaza)-5,13-dimethyl-1,9-dicadmacyclohexadecane (4b): In
a similar way to 4a, CdCl2 (1.20 g, 6.53 mmol) and 4 (0.83 g, 6.53
mmol) yielded 0.72 g (49%) of colorless fine crystalline 4b, m.p.
89°C. Although the mixture was protected from light during the
reaction, the formation of cadmium metal was observed. Ϫ 1H
NMR (C6D6): δ ϭ 0.67 (t, 3J ϭ 7.0 Hz, CdCH2), 1.89 (s, CH3),
Bis[2,6-bis(diethylaminomethyl)phenyl]zinc (3a): A solution of 3
(1.07 g, 4.2 mmol) in Et2O (40 ml) was mixed in portions with
ZnCl2 (0.29 g, 2.1 mmol). The reaction mixture warmed up slightly.
After stirring for 16 h at room temperature the solvent was removed
in vacuo. The remaining solid was suspended in n-pentane. The
mixture was filtered through a fine glass frit, and the filtrate volume
was reduced to about 20 ml. Storing at Ϫ20°C yielded 0.82 g (70%)
of colorless fine crystalline 3a, m.p. 102°C. Ϫ 1H NMR (C6D6):
3
3
2.01 (quint, J ϭ 6.9/6.6 Hz, CH2), 2.25 (t, J ϭ 6.5 Hz, CH2N).
Ϫ
13C NMR (C6D6): δ ϭ 12.14 (CdCH2), 32.56 (CH2), 41.93
(CH3), 61.89 (CH2N). Ϫ MS; m/z (%): 454 (<1) [M(114Cd)ϩ], 227
(3) [1/2 M(114Cd)ϩ], 114 (3) [Cdϩ], and others as for 4a. Ϫ
C14H30Cd2N2 (451.21): calcd. C 37.27, H 6.70, N 6.21; found C
37.01, H 6.58, N 6.34.
(5,13-Diaza)-5,13-dimethyl-1,9-dimercuracyclohexadecane (4c):
In a similar way to 4a, HgCl2 (0.14 g, 0.51 mmol) and 4 (0.065 g,
0.51 mmol) yielded 0.23 g (72%) of colorless crystalline 4c, m.p.
97°C. Ϫ 1H NMR (C6D6): δ ϭ 0.99 (t, 3J ϭ 6.9 Hz, HgCH2), 1.91
3
3
δ ϭ 0.85 (t, J ϭ 7.1 Hz, CH3), 2.63 (q, J ϭ 7.1 Hz, CH3CH2),
3.74 (s, CH2Caryl), 7.29-7.43 (m, CHaryl). Ϫ 13C NMR (C6D6): δ ϭ
10.35 (CH3), 46.09 (CH3CH2), 63.42 (CH2Caryl), 124.85 (C-3,5),
126.68 (C-4), 147.54 (C-2,6), 158.44 (C-1). Ϫ MS; m/z (%): 558 (15)
[M(64Zn)ϩ], 529 (3) [Mϩ Ϫ C2H5], 310 (17) [ZnC6H3(CH2-
3
3
(s, CH3), 2.06 (quint, J ϭ 6.9/6.5 Hz, CH2), 2.25 (t, J ϭ 6.5 Hz,
CH2N). Ϫ 13C NMR (C6D6): δ ϭ 27.58 (HgCH2), 37.56 (CH2),
41.95 (CH3), 62.20 (CH2N). Ϫ MS; m/z (%): 627 (<1) [Mϩ], 315
(<1) [1/2 M(202Hg)ϩ], 202 (4) [Hgϩ], and others as for 4a. Ϫ
C14H30Hg2N2 (627.59): calcd. C 26.79, H 4.82 N, 4.46; found C
26.68, H 4.80, N 4.73.
NEt2)2ϩ], 247 (100) [C6H3(CH2NEt2)2ϩ], and others.
Ϫ
C32H54N4Zn (560.20): calcd. C 68.61, H 9.72, N 10.00; found C
68.40, H 9.69, N 10.11.
Bis[2,6-bis(diethylaminomethyl)phenyl]cadmium (3b): In a simi-
lar way to 3a, CdCl2 (0.21 g, 1.14 mmol) was mixed with 3 (0.58
g, 2.28 mmol) and yielded 0.43 g (62%) of colorless crystals of 3b,
m.p. 137°C. Although the mixture was protected from light during
Bis[3-(N-piperidino)propyl]zinc (5a): ZnCl2 (0.43g, 3.19 mmol)
was added portionwise to a suspension of 5 (0.85g, 6.38 mmol) in
Et2O (50 ml). The cloudy reaction mixture was stirred at room
temperature for 18 h. After removing the solvent and addition of
n-pentane, the mixture was filtered through a fine glass frit. The
pale yellow filtrate was concentrated to a volume of about 30 ml
and yielded, after storing at Ϫ20°C, 0.77 g (76%) of colorless crys-
talline 5a, m.p. 80°C. Ϫ 1H NMR (C6D6): δ ϭ 0.48 (t. 3J ϭ 7.1
1
the reaction, the formation of cadmium metal was observed. Ϫ H
NMR (C6D6): δ ϭ 0.86 (t, 3J ϭ 7.2 Hz, CH3), 2.61 (q, 3J ϭ 7.1
Hz, CH3CH2), 3.49 (s, CH2Caryl), 7.08-7.33 (m, CarylH). Ϫ 13C
NMR (C6D6): δ ϭ 10.27 (CH3), 45.81 (CH3CH2), 63.52 (sat.,
CH2Caryl), 124.51 (C-3,5), 126.01 (C-4), 147.54 (sat., C-2,6), 163.69
(C-1). Ϫ 113Cd NMR (C6D6): δ ϭ Ϫ182.58. Ϫ MS; m/z (%): 246
(2) [C6H3(CH2NEt2)2ϩ Ϫ H], and others as for 3a. Ϫ C32H54CdN4
(607.21): calcd. C 63.30, H 8.96, N 9.23; found C 63.08, H 8.94,
N 9.51.
3
3
Hz, ZnCH2), 1.29 (m, J ϭ 5.5 Hz, ZnCH2CH2), 1.52 [quint, J ϭ
5.6 Hz, N(CH2CH2)2CH2], 2.01 [m, 3J
ϭ
6.2 Hz,
3
3
N(CH2CH2)2CH2], 2.19 (t, J ϭ 5.6 Hz, CH2N), 2.27 [t, J ϭ 5.4
Hz, N(CH2CH2)2CH2]. Ϫ 13C NMR (C6D6): δ ϭ 8.22 (ZnCH2),
24.82 [CH2CH2N(CH2CH2)2CH2], 25.37 [N(CH2CH2)2CH2], 55.05
[N(CH2CH2)2CH2], 64.06 (CH2N). Ϫ MS; m/z (%): 316 (<1)
[M(64Zn)ϩ], 127 (8) [C5H10N(CH2)2CH3ϩ], 98 (100) [C5H10-
NCH2ϩ], and others. Ϫ C16H32N2Zn (317.84): calcd. C 60.46, H
10.15, N 8.81; found C 60.37, H 9.97, N 9.24.
Bis[2,6-bis(diethylaminomethyl)phenyl]mercury (3c): In a similar
way to 3a, HgCl2 (0.86 g, 3.17 mmol) and 3 (1.61 g, 6.33 mmol)
yielded 1.41 g (64%) of colorless crystals of 3c which melt below
1
3
room temperature. Ϫ H NMR (C6D6): δ ϭ 0.92 (t, J ϭ 7.1 Hz,
3
CH3), 2.58 (q, J ϭ 7.1 Hz, CH3CH2), 3.70 (s, CH2Caryl), 7.16 (t,
3J ϭ 7.4 Hz, C-3,5H), 7.36 (d, J ϭ 7.2 Hz, C-4H). Ϫ 13C NMR
3
Bis[3-(N-piperidino)propyl]cadmium (5b): In a similar way to 5a,
CdCl2 (0.805 g, 4.39 mmol) and 5 (1.17 g, 8.79 mmol) yielded 1.04
(C6D6):
3J(13C,199Hg) ϭ 42 Hz, CH2Caryl], 125.57 (C-3,5), 126.56 (C-4),
146.60 [sat., 2J(13C,199Hg)
22 Hz, C-2,6], 171.74 [sat.,
1J(13C,199Hg)
714 Hz, C-1]. MS; m/z (%): 696 (<1)
δ ϭ 10.13 (CH3), 45.41 (CH3CH2), 61.17 [sat.,
1
g (65%) of large colorless crystals of 5b, m.p. > 90°C (dec.). Ϫ H
NMR (C6D6): δ ϭ 0.59 (t, 3J ϭ 6.9 Hz, CdCH2), 1.31 (m, 3J ϭ
ϭ
3
ϭ
Ϫ
5.1 Hz, CdCH2CH2), 1.56 [quint, J ϭ 5.6 Hz, N(CH2CH2)2CH2],
[M(202Hg)ϩ], 623 (2) [Mϩ Ϫ NEt2], 247 (100) [C6H3(CH2NEt2)2ϩ],
202 (1) [Hgϩ], and others as for 3a. Ϫ C32H54HgN4 (695.40): calcd.
C 55.27, H 7.83, N 8.06; found C 54.84, H 8.00, N 8.07.
2.04 [m, N(CH2CH2)2CH2], 2.14-2.19 [m, CH2N(CH2CH2)2CH2].
1
Ϫ
13C NMR (C6D6): δ ϭ 13.29 [sat., J(13C,111/113Cd) ϭ 307/294
Hz, CdCH2], 24.94 [N(CH2CH2)2CH2], 25.88 [N(CH2CH2)2CH2],
26.31 [sat., 2J(13C,113Cd)
15.4 Hz, CdCH2CH2), 55.38
[N(CH2CH2)2CH2], 64.30 [sat., 3J(13C,113Cd) ϭ 14.7 Hz, CH2N].
MS; m/z (%): 366 (<1) [M(114Cd)ϩ], 240 (5)
[C5H10N(CH2)3Cdϩ], and others as for 5a.
C16H32CdN2
ϭ
(5,13-Diaza)-5,13-dimethyl-1,9-dizincacyclohexadecane (4a):
4
(2.04 g, 16.05 mmol) was dissolved in Et2O (150 ml) and mixed in
portions with ZnCl2 (2.19 g, 16.05 mmol). The reaction mixture
warmed up slightly and a white precipitate formed. After stirring
at room temperature for 12 h the solvent was removed in vacuo.
The remaining solid was suspended in n-pentane and filtered
through a fine glass frit. The filtrate volume was reduced to about
50 ml. Storing at Ϫ20°C yielded 2.15 g (75%) of large colorless
Ϫ
Ϫ
(364.85): calcd. C 52.67, H 8.84, N 7.68; found C 53.28, H 8.51,
N 8.36.
Bis[3-(N-piperidino)propyl]mercury (5c): In a similar way to 5a,
HgCl2 (1.09 g, 4.01 mmol) and 5 (1.07 g, 8.03 mmol) yielded 1.06
Eur. J. Inorg. Chem. 1998, 245Ϫ252
251