P.B. Hitchcock et al. / Journal of Organometallic Chemistry 694 (2009) 667–676
675
Table 7
Crystal data and refinement details for compounds 2–7 and 9.
2
3
4
5
6
7
9
Empirical formula
M
Crystal system
Space group
a (Å)
C42H58FeN4Si4
787.13
C42H58N4NiSi4
789.99
C30H26N4Ni 2(C4H10O)
C42H58CuN4Si4
794.82
C30H26CuN4 2(C4H10O)
C42H58N4PdSi4
837.68
C24H34N2PdSi2
513.11
649.50
Orthorhombic
Pbca (No. 61)
11.264(6)
17.225(15)
18.337(16)
90
90
90
3558(5)
4
654.33
Orthorhombic
Pbca (No. 61)
11.168(5)
17.299(4)
18.675(6)
90
90
90
3608(2)
4
Triclinic
Monoclinic
P21/n (No. 14)
12.788(12)
17.482(8)
20.623(9)
90
104.23(6)
90
4469(5)
4
Monoclinic
P21/n (No. 14)
12.814(3)
17.491(4)
20.599(5)
90
104.21(2)
90
4475.6(18)
4
Triclinic
Triclinic
ꢀ
ꢀ
ꢀ
P1 (No. 2)
P1 (No. 2)
P1 (No. 2)
12.346(3)
13.222(2)
14.370(3)
80.75(2)
77.48(2)
83.84(2)
2253.8(8)
2
9.816(5)
11.087(4)
11.995(4)
115.63(3)
113.10(3)
89.89(3)
1060.2(8)
1
12.818(4)
12.436(4)
18.731(6)
79.85(2)
83.32(3)
69.01(2)
2603.3(15)
4
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
U (Å3)
Z
F (000)
840
0.47
5483
3547
0.054
0.105
0.105, 0.125
1688
0.57
5474, 0.115
2284
0.083
1384
0.58
2064
717
0.094
0.197
0.265, 0.283
1692
0.63
7849
3216
0.107
0.228
0.256, 0.292
1388
0.64
5238
1975
0.073
0.131
0.218, 0.181
440
0.59
2600
2134
0.047
0.103
0.065, 0.111
1064
0.82
15140
9758
0.049
0.100
0.091, 0.117
l
(Mo K
Unique reflections, [Rint
Reflections with [I > 2 (I)]
R1 [I > 2 (I)]
wR2 [I > 2 (I)]
Rindices (all data) R1, wR2
a
) (mmꢀ1
)
]
r
r
r
0.148
0.213, 0.201
sion was allowed to warm to room temperature and was stirred for
a further 12 h, a deep red suspension being obtained. The mixture
was filtered and the residual red brick solid was washed with
diethyl ether (15 cm3) and pentane (15 cm3) and dried in vacuo;
crystals of 7 (1.33 g, 65%). Anal. calc. for C42H58N4PdSi4 requires:
60.2; H, 6.98; N, 6.68. Found: C, 52.9; H, 6.41; N, 6.52%. M.p.
172–173 °C decomp., were isolated. 1H NMR (CDCl3): d 0.23 (s,
Si(CH3)3, 36 H), 5.86 (s, CH, 2 H), 7.30–7.38 (m, Ph, 12 H), 7.54–
7.58 ppm (m, Ph, 8 H). 13C{1H} NMR (CDCl3): d 4.7 (s, Si(CH3)3),
121.2 (s, CH), 127.6 (s, Ph, o- or m-CH), 129.3 (s, Ph, p-CH), 130.0
(s, Ph, o- or m-CH), 141.5 (s, Ph, Cipso) and 175.1 ppm (s, CN). MS,
m/z (%, assignment): 836 (5, [M]+); 471 (12, [M–L]+); 365 (8, [L]+).
Crystals of 7 suitable for X-ray analysis were obtained from
toluene.
6.70; N, 5.44%. M.p. 90–92 °C. 1H NMR (C6D6): d 0.01 (s, Si(CH3)3, 18
3
3
H), 2.35 (d, JHH = 12.3, CH2CHCH2, 2 H), 3.49 (d, JHH = 7.0,
3
CH2CHCH2, 2 H), 4.90 (tt, JHH = 12.3 and 7.0 Hz, CH2CHCH2, 1 H),
5.56 (s, CH, 1 H), 7.05–7.10, (m, Ph, 6 H), 7.55–7.60 ppm (m, Ph,
4 H). 13C{1H} NMR (C6D6): d 5.1 (s, Si(CH3)3), 55.4 (s, CH2CHCH2),
111.5 and 112.3 (s, CH2CHCH2 and CH), 126.3 (s, Ph, p-CH), 128.2
(s, Ph, o- or m-CH), 129.1 (s, Ph, o- or m-CH), 145.9 (s, Ph, Cipso
)
and 172.0 ppm (s, CN). MS, m/z (%, assignment): 512 (11, [M]+);
471 (47, [MꢀC3H5]+); 365 (69, [L]+).
3.11. [Ni{g
3-C3H5}({N(SiMe3)C(Ph)}2CH)] (10)
[Li({N(SiMe3)C(Ph)}2CH)]2 (0.63 g, 0.85 mmol) in tetrahydrofu-
ran (ca. 10 cm3) was added slowly to a solution of [{Ni(g3
C3H5)(
-Br)}2] (0.31 g, 0.86 mmol) in tetrahydrofuran (ca. 15 cm3)
-
l
3.9. [Pd({N(SiMe3)C(Ph)}2CH)(
l
-Cl)]2 (8)
at 0 °C. The mixture was allowed to warm to room temperature
and stirred for a further 2 h, a deep purple solution being obtained.
Tetrahydrofuran was removed in vacuo and the residue was
‘‘stripped” with hexane (2 ꢄ 20 cm3) and then extracted into hex-
ane. The extract was filtered. The filtrate was concentrated to ca.
5 cm3 and cooled to ꢀ30 °C, yielding deep red-violet crystals
(0.38 g). A second crop of crystals of 10 was obtained from the
mother liquor (0.35 g, combined yield 73%). Anal. Calc. for
C24H34N2NiSi2 requires: C, 61.9; H, 7.36; N, 6.02). Found: C, 60.2;
H, 7.16; N, 5.97%. M.p. 89–92 °C. 1H NMR (C6D6): d 0.15 (s, Si(CH3)3,
A solution of [Li({N(SiMe3)C(Ph)}2CH)]2 (0.54 g, 0.73 mmol) in
diethyl ether (25 cm3) was added to a suspension of [PdCl2(cod)]
(0.41 g, 1.44 mmol) in thf (20 cm3) at 0 °C. The resulting deep pur-
ple mixture was stirred for 30 min. The solvent was removed in va-
cuo, the residue ‘‘stripped” with diethyl ether (20 cm3) and then
dissolved in diethyl ether (2 ꢄ 20 cm3). Filtration from a dark pre-
cipitate followed by evaporation of the volatiles from the filtrate
yielded the deep green solid 8 which was washed with hexane
and dried in vacuo (0.18 g, 25%), mp. 219–222 °C. 1H NMR (C6D6):
d 0.58 (s, Si(CH3)3, 36 H), 5.60 (s, CH, 2 H), 7.01 (br m, Ph, 12 H),
7.45 ppm (br m, Ph, 8 H). 13C{1H} NMR (C6D6): d 6.1 (s, Si(CH3)3),
119.4 (s, CH), 126.6, 128.0, 129.9 (s, Ph, o-, m- and p-CH), 139.2
(s, Ph, Cipso) and 172.3 ppm (s, CN). MS, m/z (%, assignment):
1012 (3, [M]+); 836 (5, [PdL2]+); 690 (19, [PdL2ꢀ2SiMe3]+); 365
(8, [L]+).
3
3
18 H), 1.59 (d, JHH = 15.8, CH2CHCH2, 2 H), 2.73 (d, JHH = 8.5,
3
CH2CHCH2, 2 H), 5.1 (pent, JHH = 7.9 Hz, CH2CHCH2, 1 H), 6.04 (s,
CH, 1 H), 7.07–7.10 (m, Ph, 6 H), 7.51–7.54 ppm (m, Ph, 4 H).
13C{1H} NMR (C6D6): d 5.5 (s, Si(CH3)3), 49.6 (s, CH2CHCH2), 106.1
and 112.3 (s, CH2CHCH2), 116.7 (s, CH), 125.8 (s, Ph, o- or m-CH),
128.6 (s, Ph, p-CH), 128.9 (s, Ph, o- or m-CH), 144.9 (s, Ph, Cipso
)
and 172.0 ppm (s, CN). MS, m/z (%, assignment): 464 (28, [M]+);
423 (53, [M–C3H5]+); 365 (7, [L]+).
3.10. [Pd{g
3-C3H5}({N(SiMe3)C(Ph)}2CH)] (9)
3.12. Crystal data and refinement details for 2, 3, 4, 5, 6, 7 and 9
[Li({N(SiMe3)C(Ph)}2CH)]2 (0.28 g, 0.38 mmol) in tetrahydrofu-
ran (20 cm3) was added dropwise to a solution of [{Pd(g3
C3H5)(
-Cl)}2] (0.14 g, 0.38 mmol) in tetrahydrofuran (20 cm3) at
0 °C. The resulting orange mixture was stirred for ca. 30 min. and
allowed to warm to room temperature. The solvent was removed
in vacuo, the residue ‘‘stripped” with hexane (2 ꢄ 10 cm3) and then
dissolved in hexane (10 cm3). Filtration from a white precipitate
followed by concentration of the filtrate to ca. 3–4 cm3 and cooling
to ꢀ30 °C yielded orange crystals of 9 (0.23 g, 63%). Anal. Calc. for
C24H34N2PdSi2 requires: C, 56.2; H, 6.68; N, 5.46). Found: C, 56.0; H,
-
Diffraction data were collected on a Enraf Nonius CAD-4 or for 4
a Nonius Kappa CCD diffractometer using monochromated radia-
tion, k 0.71073 Å, at 293(2) K. Crystals were mounted under argon
into Lindemann capillaries and then sealed.
For 9 there were two independent molecules in the asymmetric
unit, one of which had the allyl groups disordered ‘‘up” or ‘‘down”.
Absorption corrections, other than for 4 or 6, were applied using
psi-scans. Drawings are ORTEP-3 for Windows, with 50% ellipsoids
(hydrogen atoms are omitted for clarity). Structures were refined
l