Square-Planar 2-Toluenido(triphenylphosphane)nickel(II) Complexes
(RP)/(SP)-(SP-4-3)-[Ni(L2)(2-tol)(PPh3)] (5): (SP-4-3)-[NiBr(2- vacuo to yield 352 mg (71%) of 7. Single crystals suitable for X-
tol)(PPh3)2] (1) (754 mg, 1 mmol) was dissolved in tetrahydrofuran
(50 mL). 3-Oxo-2-pyrrolidin-(2Z)-ylidenehexanenitrile
ray diffraction were obtained by slow diffusion of a mixture of
pentane/hexane (1:1) into a concentrated solution of the complex
in toluene. 1H NMR (500.13 MHz, C6D6, room temp.): δ = 0.81
(m, 2 H, CH2-CH2-CH2), 2.43 (m, 2 H, CH2-C=C), 2.59, 2.70 (m,
(HL2)
(178 mg, 1 mmol) and subsequently Ag2O (116 mg) were added.
The resulting black suspension was stirred overnight, filtered, and
the solvent was removed in vacuo. After addition of pentane
(20 mL) and stirring overnight, a yellow precipitate formed, which
was collected and washed with pentane to yield 448 mg (76%) of
3
2 H, CH2-N-C), 2.62 (s, 3 H, CH3), 6.39 (d, JHH = 7.0 Hz, 1 H,
3
2-tol 3-H), 6.53, 6.62 (t, JHH = 7.0 Hz, 2 H, 2-tol 4,5-H), 6.95 (m,
10 H, 2-tol 6-H + PPh3), 7.49 (m, 6 H, PPh3) ppm. 13C{1H} NMR
1
3
5. H NMR (500.13 MHz, CD2Cl2, room temp.): δ = 0.53 (t, JHH (125.77 MHz, CDCl3, room temp., only aliphatic ring protons): δ
3
= 7.0 Hz, 3 H, CH2-CH3), 0.67 (m, 2 H, CH2-CH3), 1.60 (qt, JHH = 26.5 (CH2-C=C), 40.1 (CH2-CH2-CH2), 64.5 (CH2-N-C) ppm.
= 7.0 Hz, 2 H, CH2-CH2-CH2), 2.57 (s, 3 H, 2-tol CH3), 1.81 +
19F NMR (470.54 MHz, C6D6, room temp., ppm): δ = –116.4 (d,
2.07 (m, 1+ 1 H, CHHЈ-CH2-CH3), 2.78 (m, 4 H, CH2-C=C + 2JFF = 293 Hz, 1 F, 6-CFax), –117.8 (d, JFF = 294 Hz, 1 F, 2-
2
3
2
2
CH2-N-C), 6.39 (d, JHH = 7.0 Hz, 1 H, 2-tol 3-H), 6.49, 6.57 (t, CFax), –121.9 (d, JFF = 281 Hz, 1 F, 5-CFax), –122.1 (d, JFF
3JHH = 7.0 Hz, 2 H, 2-tol 4,5-H), 7.25 (m, 10 H, 2-tol 6-H + PPh3), 279 Hz, 1 F, 3-CFax), –123.5 (d, 2JFF = 283 Hz, 1 F, 4-CFax), –131.4
7.39 (m, 6 H, PPh3) ppm. 1H NMR (200.13 MHz, C6D6, room (d, JFF = 292 Hz, 1 F, 6-CFeq), –132.3 (d, JFF = 294 Hz, 1 F, 2-
=
2
2
3
2
2
temp.): δ = 0.58 (t, JHH = 7.2 Hz, 3 H, CH2-CH3), 0.83 (m, 2 H, CFeq), –139.7 (d, JFF = 279 Hz, 2 F, 3,5-CFeq), –142.2 (d, JFF
=
CH2-CH3), 0.98 (hex, 3JHH = 7.8 Hz, 2 H, CH2-CH2-CH2), 2.06 +
283 Hz, 1 F, 4-CFeq), –174.1 (hept, JFF = 37, JFF = 18 Hz, 1 F,
4
5
2.32 (m, 1+ 1 H, CHHЈ-CH2-CH3), 2.54 (m, 2 H, CH2-C=C), 2.75 C(O)CF) ppm. 19F NMR (470.54 MHz, CD2Cl2, room temp.,
2
2
(m, 2 H, CH2-N-C), 2.75 (s, 3 H, 2-tol CH3), 6.65 (m, 3 H, 2-tol ppm): δ = –116.3 (d, JFF = 293 Hz, 1 F, 6-CFax), –117.7 (d, JFF
3,4,5-H), 6.96 (m, 10 H, 2-tol 6-H + PPh3), 7.48 (m, 6 H, PPh3) = 294 Hz, 1 F, 2-CFax), –121.8 (d, JFF = 281 Hz, 1 F, 5-CFax),
2
ppm. 13C{1H} NMR (125.77 MHz, CD2Cl2, room temp., not all
carbons observed): δ = 13.5, 18.6, 21.0, 25.3, 38.2, 39.9, 62.1 ppm.
31P{1H} NMR (202.46 MHz, CD2Cl2, room temp.): δ = 28.8 ppm.
31P{1H} NMR (202.46 MHz, C6D6, room temp.): δ = 29.4 ppm.
–122.0 (d, JFF = 279 Hz, 1 F, 3-CFax), –123.3 (d, JFF = 283 Hz,
2
2
2
1 F, 4-CFax), –131.2 (d, JFF = 292 Hz, 1 F, 6-CFeq), –132.2 (d,
2JFF = 294 Hz, 1 F, 2-CFeq), –139.5 (d, JFF = 279 Hz, 2 F, 3,5-
2
2
4
CFeq), –141.9 (d, JFF = 283 Hz, 1 F, 4-CFeq), –173.9 (hept, JFF
5
IR (KBr disk): ν = 3050 (m, C–Haromat.) 2958 (m, C–Haliphat.) 2196
=
37, JFF
= 18 Hz, 1
F, C(O)CF) ppm. 31P{1H} NMR
˜
(vs, CϵN) 1574 (vs, C=O) 1478 (vs, C=C) 1435 (m, P–C) cm–1. (202.46 MHz, C6D6, room temp.): δ = 27.5 ppm. 31P{1H} NMR
C35H35N2NiOP (589.34): calcd. C 71.33, H 5.99, N 4.75; found C
71.50, H 5.95, N 4.66.
(202.46 MHz, CD2Cl2, room temp.): δ = 27.2 ppm. IR (KBr disk):
ν = 3054 (m, C–Haromat.) 2981 (m, C–Haliphat.) 2212 (vs, CϵN) 1584
˜
(vs, C=O) 1506 (vs, C=C) 1435 (m, P–C) 1242 (s, C–F) cm–1. MS
(ESI, MeOH): m/z = 849 [M + Na]+. C38H28F11N2NiOP·C7H8
(919.44): calcd. C 58.79, H 3.95, N 3.05; found C 58.51, H 3.75, N
3.23.
(SP-4-3)-[Ni(L2)(mes)(PPh3)] (6): The synthesis was carried out as
for 5, except that (SP-4-3)-[NiBr(mes)(PPh3)2] (2) (782 mg,
1
1 mmol) was used. Yield: 494 mg (80%). H NMR (200.13 MHz,
3
C6D6, room temp.): δ = 0.57 (t, JHH = 7.3 Hz, 3 H, CH2-CH3),
0.84 (sext, 3JHH = 7.5 Hz, 2 H, CH2-CH3), 1.00 (qt, 3JHH = 7.6 Hz,
(SP-4-3)-[Ni(L3)(mes)(PPh3)] (8): The synthesis was carried out as
for 7, except that (SP-4-3)-[NiBr(mes)(PPh3)2] (2) (469 mg,
0.6 mmol) was used. Yield: 436 mg (85%). 1H NMR (500.13 MHz,
3
2 H, CH2-CH2-CH2), 2.18 (s, 3 H, p-CH3), 2.29 (t, JHH = 7.4 Hz,
2 H, CH2-CH2-CH3), 2.56 (t, 3JHH = 8.0 Hz, 2 H, CH2-C=C), 2.74
3
(t, JHH = 7.4 Hz, 2 H, CH2-N-C), 2.93 (s, 6 H, o-CH3), 6.34 (s, 2
CD2Cl2, room temp.): δ = 1.65 (qt, 3JHH = 7.9 Hz, 2 H, CH2-CH2-
H, mes-H), 6.96 (m, 9 H, PPh3), 7.43 (m, 6 H, PPh3) ppm. 1H
3
CH2), 2.01 (s, 3 H, p-CH3), 2.76 (s, 6 H, o-CH3), 2.85 (t, JHH
=
3
NMR (200.13 MHz, CD2Cl2, room temp.): δ = 0.55 (t, JHH
=
3
7.5 Hz, 2 H, CH2-C=C), 2.93 (t, JHH = 8.3 Hz, 2 H, CH2-N-C),
6.4 Hz, 3 H, CH2-CH3), 0.65 (sext, 3JHH = 7.2 Hz, 2 H, CH2-CH3),
6.11 (s, 2 H, mes), 7.29 (m, 15 H, PPh3) ppm. 1H NMR
3
3
1.60 (qt, JHH = 7.7 Hz, 2 H, CH2-CH2-CH2), 2.02 (t, JHH
=
3
(500.13 MHz, C6D6, room temp.): δ = 0.83 (qt, JHH = 7.8 Hz, 2
H, CH2-CH2-CH2), 2.08 (s, 3 H, p-CH3), 2.47 (t, JHH = 8.0 Hz, 2
H, CH2-C=C), 2.63 (t, JHH = 7.3 Hz, 2 H, CH2-N-C), 2.85 (s, 6
7.8 Hz, 2 H, CH2-CH2-CH3), 2.06 (s, 3 H, p-CH3), 2.70 (s, 6 H, o-
CH3), 2.77 (m, 4 H, CH2-C=C + CH2-N-C), 6.17 (s, 2 H, mes-H),
7.28 (m, 15 H, PPh3) ppm. 13C{1H} NMR (125.77 MHz, CD2Cl2,
room temp.): δ = 13.6, 18.4, 20.0, 21.0, 25.3, 38.1, 40.0, 61.9, 80.9,
100.1, 126.0, 127.7 (d, JPC = 10 Hz), 129.8, 130.8, 131.2, 132.6,
134.3 (d, JPC = 10 Hz), 142.1, 170.4, 186.7 ppm. 31P{1H} NMR
(81.01 MHz, CD2Cl2, room temp.): δ = 25.9 ppm. 31P{1H} NMR
(81.01 MHz, C6D6, room temp.): δ = 26.4 ppm. MS (MALDI,
3
3
H, o-CH3), 6.19 (s, 2 H, mes), 7.09 (m, 15 H, PPh3) ppm. 13C{1H}
NMR (125.77 MHz, C6D5CD3, room temp., only aliphatic ring
protons): δ = 26.5 (CH2-C=C), 40.2 (CH2-CH2-CH2), 64.4 (CH2-
N-C) ppm. 19F NMR (470.52 MHz, C6D6, room temp., ppm): δ =
–116.6 (d, 2JFF = 294 Hz, 2 F, 2,6-CFax), –121.6 (d, 2JFF = 272 Hz,
2
2 F, 3,5-CFax), –123.2 (d, JFF = 283 Hz, 1 F, 4-CFax), –131.2 (d,
CH OH): m/z = 381 [PPh +mes]+. IR (KBr disk): ν = 3052 (m, C–
˜
2
2JFF = 293 Hz, 2 F, 2,6-CFeq), –139.3 (d, JFF = 279 Hz, 2 F, 3,5-
3
3
Haromat.) 2960 (m, C–Haliphat.) 2196 (vs, CϵN) 1573 (vs, C=O) 1478
(vs, C=C) 1434 (m, P–C) cm–1. C37H39N2NiOP (617.39): calcd. C
71.98, H 6.37, N 4.54; found C 72.22, H 6.06, N 4.40.
(RP)/(SP)-(SP-4-3)-[Ni(L3)(2-tol)(PPh3)] (7): 3-Oxo-2-pyrrolidin- –122.7 (d, 2JFF = 280 Hz, 2 F, 3,5-CFax), –123.9 (d, 2JFF = 281 Hz,
2
4
CFeq), –141.7 (d, JFF = 282 Hz, 1 F, 4-CFeq), –173.3 (hept, JFF
= 17 Hz, 1 F, C(O)CF) ppm. 19F NMR (470.54 MHz, CD2Cl2,
room temp., ppm): δ = –117.4 (d, JFF = 292 Hz, 2 F, 2,6-CFax),
2
(2Z)-ylidene-3-undecafluorocyclohexylpropionitrile (HL3) (250
mg, 0.6 mmol) was dissolved in toluene (30 mL). Then, sodium bi-
s(trimethylsilyl)amide (1.0 mL, 0.6 mmol, 0.6 in toluene) was
added, and the mixture was stirred overnight. A solution of (SP-
4-3)-[NiBr(2-tol)(PPh3)2] (1) (452 mg, 0.6 mmol) in toluene (30 mL)
was added dropwise with stirring. After complete addition, stirring
was continued overnight, and the reaction mixture was filtered
through Celite. The solvent was removed in vacuo, and pentane
(20 mL) was added to the residue. After stirring overnight, the yel-
low precipitate was filtered, washed with pentane and dried in
1 F, 4-CFax), –132.4 (d, JFF = 282 Hz, 2 F, 2,6-CFeq), –140.1 (d,
2
2
2JFF = 280 Hz, 2 F, 3,5-CFeq), –142.6 (d, JFF = 282 Hz, 1 F, 4-
5
CFeq), –174.7 (hept, JFF = 17 Hz, 1 F, C(O)CF) ppm. 31P{1H}
NMR (202.46 MHz, CD2Cl2, room temp.): δ = 24.6 ppm. 31P{1H}
NMR (202.46 MHz, C6D5CD3, room temp.): δ = 24.8 ppm. MS
(MALDI, CH OH): m/z = 877 [M + Na]+. IR (KBr disk): ν =
˜
3
3058 (m, C–Haromat.) 2965 (m, C–Haliphat.) 2213 (vs, CϵN) 1584
(vs, C=O) 1506 (vs, C=C) 1436 (m, P–C) 1238 (s, C–F) cm–1.
C40H32F11N2NiOP (855.35): calcd. C 56.17, H 3.77, N 3.28; found
C 56.36, H 3.57, N 2.99.
Eur. J. Inorg. Chem. 2010, 1670–1678
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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