P. Braunstein et al. / Journal of Organometallic Chemistry 582 (1999) 371–377
375
H, 5.2; N, 5.0. C31H26ClN2P (493.0) Calc.: C, 75.53; H,
5.31; N, 5.68%. Spectroscopic data are identical with
those of 3·HBr.
3.2.6. [N¸iP¹h¹{¹Ph¹2¹P¹N¹ꢀ¹Cº(NPh)Ph}(PMe2Ph)] (6b)
As described for 6a, 0.38 g (1.4 mmol) [Ni(COD)2] in
25 ml toluene was reacted with a solution of 199 ml (1.4
mmol)
PMe2Ph
and
0.64
g
(1.4
mmol)
3.2.3. Ph3PꢀNC(ꢀNPh)Ph (3)
Ph3PꢀNC(ꢀNPh)Ph in 20 ml toluene. The residue ob-
tained at the end of the reaction was treated with 10 ml
toluene and the suspension filtered. The solid was
washed with 2×5 ml pentane and dried in vacuo to
afford pure 6b. Yield 0.45 g (50%). Anal. Found: C,
70.90; H, 5.65; N, 4.32; P, 9.27. C39H36N2P2 Ni (653.4)
A solution of 2.83 g (5.3 mmol) 3·HBr in 25 ml
CH2Cl2 was stirred with 0.68 g (17.0 mmol) powdered
NaOH for 4 h at ambient temperature. After filtration,
the solvent was removed in vacuo to give the analyti-
cally pure product. Yield 2.45 g (\98%). Anal. Found:
C, 80.86; H, 5.50; N, 6.03; P, 6.83. C31H25N2P (456.5)
1
Calc.: C, 71.69; H, 5.55; N, 4.29; P, 9.48%. H NMR
1
Calc.: C, 81.56; H, 5.52; N, 6.14; P, 6.78%. H NMR
(C6D6): l 8.5–7.3 (30H, aromatic H), 1.42 (d, br,
2JPH:8, 6H, PMe2Ph). 31P{1H} NMR (C6D6): AB spin
system lA 68.4, lB−12.9 (2JAB=285.3). MS (EI): m/e
653 [M+], 576 [M+ −Ph], 515 [M+ –PMe2Ph], 438
[M+ –Ph–PMe2Ph].The by-product 5 could be precipi-
tated from the solution by addition of 80 ml pentane.
Yield 0.15 g (14%).
(CDCl3): l 8.2–6.1 (aromatic H). 31P{1H} NMR
(CDCl3): l 14.9 (s).
¸¹¹¹¹¹¹¹¹¹º
3.2.4. [NiPh{Ph2PNꢀC(NPh)Ph}{NPh[ꢀCPh
(NꢀPPh3)]}] (5)
A cold solution of 0.30 g (1.1 mmol) [Ni(COD)2] in
20 ml toluene was added slowly to a solution of 0.33 g
(1.1 mmol) PTol3 and 0.50
¸¹¹¹¹¹¹¹¹¹º
3.2.7. [NiPh{Ph2PNꢀC(NPh)Ph}(PMePh2)] (6c)
g
(1.1 mmol)
Ph3PꢀNC(ꢀNPh)Ph in 15 ml toluene at 0°C. The mix-
ture became dark red immediately. After stirring for 16
h at room temperature, the clear red solution was
heated to 50°C for 2 h and subsequently the solvent
was removed in vacuo. The dark residue was taken up
in 10 ml toluene, the brown solution filtered and 100 ml
pentane was added. The fluffy yellow precipitate was
filtered off, washed with 2×5 ml pentane and dried in
vacuo. A second crop of 5 could be isolated from the
solution after cooling to −18°C. Yield 0.46 g (45%).
1H NMR (C6D6): 8.4–6.1 (aromatic H). 31P{1H} NMR
(C6D6): l 78.9 (s), 3.4 (s). MS (EI): m/e 971 [M+], 894
[M+ −Ph], 515 [M+ –3], 438 [M+ –Ph–3], 456 (3+).
As described for 6a, 0.38 g (1.4 mmol) [Ni(COD)2] in
25 ml toluene was reacted with a solution of 260 ml (1.4
mmol)
PMePh2
and
0.64
g
(1.4
mmol)
Ph3PꢀNC(ꢀNPh)Ph in 20 ml toluene. 6c was obtained
as the minor product in a mixture with 5. 31P1H MNR
(C6D6): AB spin system lA 66.0, lB 1.4 (2JAB=282.9).
¸¹¹¹¹¹¹º
3.2.8. [NiPh{Ph2PNꢀ C[N(o-C6H4)NMe]}(PTol3)] (9)
»¹¹¹¹¹¹¹¹¹¼
As described for 6a, 0.41 g (1.5 mmol) [Ni(COD)2] in
30 ml toluene was reacted with a solution of 0.47 g (1.5
mmol) PTol3 and 0.55
g (1.3 mmol) Ph3PꢀNꢁ
¸¹¹¹¹¹¹¹º
C[ꢀN(o-C6H4)NMe] in 20 ml toluene. Recrystallization
from toluene/pentane gave the product, which still con-
tained some of the starting phosphorane and PTol3 due
3.2.5. [N¸iP¹h¹{¹Ph¹2¹P¹N¹ꢀ¹Cº(NPh)Ph}(PMe3)] (6a)
1
to their similar solubility properties. H NMR (C6D6):
A cold solution of 0.51 g (1.9 mmol) [Ni(COD)2] in
30 ml toluene was added slowly to a solution of 197 ml
l 8.4–6.3 (aromatic H), 3.28 (s, br, NMe), 1.90 (s, br,
PC6H4Me). 31P{1H} NMR (C6D6): AB spin system lA
67.6, lB 22.5 (2JAB=280.7). MS (EI): m/e 770 [M+],
693 [M+ −Ph], 466 [M+ −PTol3], 389 [M+ −Ph−
PTol3], 304 [PTol3+].
(1.9 mmol) PMe3 and 0.87
g
(1.9 mmol)
Ph3PꢀNC(ꢀNPh)Ph in 20 ml toluene at 0°C. The mix-
ture became yellow/orange immediately and acquired
an intense orange tint within 1 h. After 16 h stirring at
room temperature, the clear yellow/brown solution was
heated to 50°C for 2 h and subsequently the solvent
was removed in vacuo The orange residue was taken up
in 5 ml toluene, the brown solution filtered and 80 ml
pentane was added. The fluffy yellow solid was filtered
off and discarded. At −18°C, orange crystals were
precipitated from the solution. These were isolated,
washed with 2×5 ml pentane and dried in vacuo. Yield
0.27 g (26%). Anal. Found: C, 68.34; H, 5.92; N, 4.52;
P, 10.3. C34H34N2P2Ni (591.3) Calc.: C, 69.06; H, 5.80;
3.2.9. [¸N¹i2¹{P¹h¹3P¹ꢀ¹NºꢁC[¸ꢀ¹N¹(o¹-¹C¹6H¹4º)N]}4] (10)
A col»d¹so¹l¹tio¹n¹¹of¹0¹.4¹8¹g¹(¹1¹.7¹m¹m¹o¼l) [Ni(COD)2] in 30
ml toluene was added slowly to a suspension of 0.45 g
(1.7 mmol) PPh3 and 0.67 g (1.7 mmol) Ph3PꢀN−
¸¹¹¹¹¹¹¹¹º
C[ꢀN(o−C6H4)NH] in 20 ml toluene at 0°C. The mix-
ture became orange/brown immediately. After stirring
for 24 h at room temperature, the brown mixture was
filtered, the bright yellow solid washed with 2×5 ml
pentane and dried in vacuo. Owing to similar solubility
properties of some unidentified minor impurities, the
product was not obtained in a pure form. 31P{1H}
NMR (CDCl3): l 68.0 (br). MS (EI): m/e 1684 [Ni2L4+,
not observed], 1160 [Ni2L4+ −2PPh3], 1292 [Ni2L3+],
900 [Ni2L2+], 842 [NiL2+], 392 [L+].
1
N, 4.74; P, 10.48%. H MNR (C6D6): l 8.3–6.1 (25H,
2
aromatic H), 0.23 (d, JPH=7.9, 9H, PMe3). 31P{1H}
MNR (C6D6): AB spin system lA 68.7, lB −25.7
(2JAB=290.8). MS (EI): m/e 591 [M+], 514 [M+ –Ph],
515 [M+ –PMe3], 438 [M+ –Ph–PMe3].