850
M. Said et al. / Polyhedron 25 (2006) 843–852
NMR (300.13 MHz): d 0.31 (t, JP–H = 37 Hz, PtMe2),
1.74 (m, THF), 3.58 (m, THF), 7.20–7.73 (Ph). 31P
NMR (121.49 MHz): d 29.77 (t, JPt–P = 740 Hz).
4.7. Preparation of Me3SiN(PPh2)2Ni(COD), NiSi
To a mixture of Me3SiN(PPh2)2 (0.50 g, 1.09 mmol)
and Ni(COD)2 (0.30 g, 1.09 mmol) in a round bottomed
flask was added THF (30 mL). The solution was stirred
at room temperature for 5 h. The solution was concen-
trated to 5 mL and light petroleum was added (10
mL). Cooling to ꢀ26 ꢁC gave red crystals, yield 0.45 g
(66%). Anal. Calc. for C35H41NNiP2Si: C, 67.32; H,
4.4. Preparation of Me3SnN(PPh2)2 (2)
To a solution of (THF)3LiN(PPh2)2 (2.9 g, 4.77
mmol) in THF (30 mL) was added Me3SnCl (0.95 g,
4.77 mmol) in small portions using a bent finger. The
reaction was complete within 1 h. The solvent was
removed and the product extracted with light petroleum
(50 mL) to give white microcrystals, yield 2.2 g (84%).
1H NMR (300.13 MHz, C6D6): d 0.26 (s, SnMe3),
7.01–7.67 (Ph). 13C{1H} NMR (75.46 MHz): d ꢀ1.31
(s, Me), 129.00–143.39 (Ph). 31P NMR (121.49 MHz):
d 61.24.
1
6.62; N, 2.42. Found: C, 66.94; H, 6.69; N, 2.12%. H
NMR (300.13 MHz, C6D6): d ꢀ0.30 (s, SiMe3), 2.32
(s, CH2), 4.64 (s, CH), 7.14–8.01 (Ph). 13C{1H} NMR
(75.46 MHz): d 36.18 (s, CH2), 83.04 (s, CH), 127.89–
140.08 (Ph). 31P NMR (121.49 MHz): d 82.84.
4.8. Preparation of Me3SiN(PPh2)2PdCl2 and formation
of [PdCl(dppa)]2 Æ 3CH2Cl2
4.5. Preparation of Me3SnN(PPh2)2Ni(COD), NiSn
A mixture of Me3SiN(PPh2)2 (0.21 g, 0.46 mmol) and
PdCl2(COD)2 (0.13 g, 0.46 mmol) in THF (15 mL) was
stirred overnight at 20 ꢁC. The product was poorly soluble
in THF and was isolated by filtration as a yellow powder,
yield 0.22 g (76%). Anal. Calc. for C27H29Cl2NP2PdSi: C,
51.08; H, 4.60; N, 2.21; Cl, 11.17. Found: C, 51.35; H,
4.47; N, 2.18; Cl, 11.22%. 1H NMR (300.13 MHz, THF-
d8): d 0.41 (s, SiMe3), 7.30–8.14 (Ph). 31P NMR (121.49
MHz, THF-d8): d ꢀ35.85.
Method 1: A mixture of 2 (1.0 g, 1.82 mmol) and Ni
(COD)2 (0.50 g, 1.82 mmol) in THF (30 mL) was stirred
for 3 h at 25 ꢁC. The solvent volume was reduced to 10
mL, and crystallisation was initiated by adding light
petroleum (ca. 30 mL). On cooling to ꢀ26 ꢁC the prod-
uct was obtained as red crystals, yield 0.95 g (73%).
Anal. Calc. for C35H41NNiP2Sn: C, 58.79; H, 5.78; N,
1
1.96. Found: C, 58.57; H, 5.91; N, 1.86%. H NMR
Attempts to recrystallise the complex from a large
amount of THF in the presence of dichloromethane
over a period of two weeks led to the isolation of a
few crystals of the Pd(I)–dppa complex [PdCl(dppa)]2 Æ
3CH2Cl2 which was identified by X-tray diffraction.
(300.13 MHz): d ꢀ0.27 (s, Me3Sn), 2.38 (br, CH2),
4.77 (br, CH), 7.12–7.93 (Ph). 13C{1H} NMR (75.46
MHz): d ꢀ2.70 (s, Me3Sn), 28.50 (s, CH2), 85.07 (s,
CH), 128.94–142.20 (Ph). 31P NMR (121.49 MHz): d
83.67.
Method 2: To a suspension of NiLi (0.32 g, 0.41
mmol) in toluene (20 mL) was added Me3SnCl (0.08 g,
0.41 mmol) in small portions using a bent finger.
The mixture was stirred overnight at room temperature
and filtered. The solvent volume was reduced to
ca. 5 mL and light petroleum was added (3 mL) to
give a product identical to that from method 1 (0.15 g,
51%).
4.9. X-ray crystallography
Crystals were mounted on glass fibres and fixed in
the cold nitrogen stream on a Rigaku R-Axis IIc image
plate diffractometer equipped with a rotating anode
X-ray source (Mo Ka radiation) and graphite mono-
chromator. Data were collected at 140(1) K and
processed using the DENZO/SCALEPACK [8] pro-
grams. The structures were determined by the direct
methods routines in the SHELXS program [9] and refined
by full-matrix least-squares methods, on F2ꢁs, in SHELXL
[9]. Non-hydrogen atoms were refined with anisotropic
thermal parameters, and hydrogen atoms were included
in idealised positions with their Uiso values set to ride
on the Ueq values of the parent carbon and nitrogen
atoms. Scattering factors for neutral atoms were taken
from reference [10]. Computer programs used in this
analysis have been noted above or in Table 4 of [11],
and were run on a Silicon Graphics Indy at the Univer-
sity of East Anglia, or a DEC-AlphaStation 200 4/100
in the Biological Chemistry Department, John Innes
Centre.
4.6. Preparation of Me3SiN(PPh2)2PtMe2 Æ 0.5 toluene,
PtSi
A mixture of Me3SiN(PPh2)2 (0.34 g, 0.74 mmol) and
PtMe2(COD)2 (0.25 g, 0.74 mmol) in THF (20 mL) was
stirred for 3 h at room temperature. The solvent volume
was reduced to 2 mL, and light petroleum (30 mL) and
toluene (2 mL) were added to induce crystallisation. Red
microcrystals formed on cooling to ꢀ26 ꢁC, yield 0.35 g
(61%). Anal. Calc. for C29H35NP2PtSi Æ 0.5C7H8: C,
55.80; H, 5.59; N, 1.90. Found: C, 54.98; H, 5.49; N,
1.81%. 1H NMR (300.13 MHz): d ꢀ0.39 (s, SiMe3),
1.47 (t, JP–H = 36.7 Hz PtMe2), 7.03–8.05 (Ph). 31P
NMR (121.49 MHz): d 35.00 (t, JPt–P = 769.9 Hz).
Crystal data are collected in Table 8.
Said, Musa
