952
T. Haas et al. / Journal of Organometallic Chemistry 696 (2011) 946e955
3.12. (
h
5-Cyclopentadienyl)(3-dimethylamino-3-methoxy-1,2-
7.61e7.67 (m, 6H, C6H5), 8.17 (d, 4JHH ¼ 2.0 Hz, 1H, Pyr-H). 13C NMR
2
propadienylidene)(triphenylphosphane)nickel(II)
trifluormethansulfonate (6b)
(100 MHz, CD2Cl2):
d
¼ 93.4 (d, JPC ¼ 2.0 Hz, Ca), 93.3 (d,
1JPC ¼ 2.0 Hz, Cp), 98.4 (d, 3JPC ¼ 47.3 Hz, Cb), 116.3127.6, 137.9, 144.9
2
(Pyr-C), 128.8 (d, JPC ¼ 10.4 Hz, C6H5), 130.4 (C6H5), 131.4 (d,
The green powder is obtained in quantitative yield. IR (CH2Cl2,
3JPC ¼ 2.4 Hz, C6H5), 133.3 (s, C6H5), 134.4 (d, 1JPC ¼ 11.1 Hz, C6H5),
cmꢀ1):
n
(CCC) ¼ 2070 s. 1H NMR (400 MHz, CDCl3):
d
¼ 2.86 (s, 3H,
150.2 (Cg). 31P NMR (161 MHz, CDCl3):
d
¼ 41.2. UVeVIS lmax (log
3)
NCH3), 2.99 (s, 3H, NCH3), 3.48 (s, 3H, OCH3), 5.21 (s, 5H, Cp),
[Solv]: 345 nm (3.878) [CH2Cl2]. FAB-MS m/z (%): 567 (12) [Mþ], 488
(2) [(M-Br)þ], 385 (9) [(M-C7H3BrN)þ], 320 (8) [(M-C12H8BrN)þ],
263 (18) [(M-C7H3BrNNi)þ]. Anal. Calc. for C30H24BrNNiP (567.08):
C, 63.54; H, 4.09; N, 2.47. Found: C, 61.38; H, 4.04; N, 2.63.
7.35e7.48 (m, 9H, C6H5), 7.51e7.63 (m, 6H, C6H5). 13C NMR
(100 MHz, CDCl3):
d
¼ 37.6 (NCH3), 41.5 (NCH3), 60.6 (OCH3), 94.2
(Cp), 102.9 (Cb),121.1 (d, 1JCF ¼ 321.1 Hz, CF3), 129.0 (d, 2JPC ¼ 10.7 Hz,
4
C6H5), 131.5 (d, JPC
¼
2.5 Hz, C6H5), 132.0 (Cg), 132.7 (d,
3JPC ¼ 9.9 Hz, C6H5), 133.8 (d, JPC ¼ 11.3 Hz, C6H5), 154.4 (d,
3.16. (h
5-Cyclopentadienyl)(N-ethyl-3-pyridin-
1,2-propadienylidene)(triphenylphosphine)nickel(II)
tetrafluoroborate (10)
1
2JPC ¼ 24.0 Hz, Ca). 31P NMR (161 MHz, CDCl3): 44.3. 19F NMR
(376 MHz, CDCl3):
d
¼ ꢀ78.7. UVeVIS lmax (log
3) [Solv]: 398 nm
(3.697) [CH2Cl2]. FAB-MS m/z (%): 496 (100) [Mþ], 385 (16) [(M-
C6H9NO)þ], 320 (20) [(M-C11H14NO)þ], 263 (25) [PPh3]. Anal. Calc.
for C30H29F3NNiO4PS (646.28): C, 55.75; H, 4.52; N, 2.17. Found: C,
56.29; H, 4.68; N, 1.93.
Complex 10 was synthesized from alkynyl complex 8 analo-
gously to the complexes 5ae7a, however, using 1 eq of [Et3O]BF4
instead of [Me3O]BF4. Blue powder. Yield: 0.29 g (47%). Mp 63 ꢁC. IR
(CH2Cl2, cmꢀ1):
d
n
(CCC) ¼ 2072 s. 1H NMR (400 MHz, CD2Cl2):
3.13. (
h
5-Cyclopentadienyl)(3-methoxy-3-phenyl-1,2-
¼ 0.98 (t, 3H, CH3), 3.89 (q, 3JHH ¼ 6.1 Hz, 2H, CH2), 5.22 (s, 5H, Cp),
propadienylidene)(triphenylphosphane)nickel(II)
trifluormethansulfonate (7b)
6.93, 7.55, 7.80, 8.14 (4H, Pyr-H), 7.25e7.42 (9H, C6H5), 7.57e7.68
(6H, C6H5). 13C NMR (100 MHz, CDCl3):
d
¼ 14.3 (CH3), 15.5 (CH2),
94.2 (Cp), 108.0 (d, 3JPC ¼ 1.0 Hz, Cb), 122.7, 138.2, 141.4, 141.8 (4 Pyr-
C), 129.2 (d, 3JPC ¼ 10.7 Hz, P-C6H5), 130.3 (d, 1JPC ¼ 11.7 Hz, P-C6H5),
Green powder. Yield: 0.34
g
(55%). IR (CH2Cl2, cmꢀ1):
4
2
n
(CCC) ¼ 2024 s. 1H NMR (400 MHz, CDCl3):
d
¼ 3.99 (s, 3H, OCH3),
131.6 (d, JPC ¼ 2.8 Hz, P-C6H5), 132.2 (Cg), 134.3 (d, JPC ¼ 11.3 Hz,
5.20 (s, 5H, Cp), 7.22e7.70 (m, 20H, C6H5). 13C NMR (100 MHz,
P-C6H5), 146.7 (d, JPC ¼ 21.1 Hz, Ca). 31P NMR (161 MHz, CDCl3):
2
CD2Cl2):
d
¼ 16.8 (C7), 21.9 (C9), 22.4 (C10), 23.7 (C5), 25.9 (C8), 32.0
d
¼ 43.1. 19F NMR (376 MHz, CDCl3):
d
¼ ꢀ152.8. UVeVIS lmax (log
3)
(C3), 35.6 (C4), 41.8 (C2), 47.9 (C6), 65.9 (OMe), 73.2 (C1), 94.1 (Cp),
[Solv]: 459 nm (3.643) [CH2Cl2]. FAB-MS m/z (%): 517 (21) [Mþ], 385
(14) [(M-C9H9N)þ], 320 (14) [(M-C9H9N-C5H5)þ]. Anal. Calc. for
C32H29BF4NNiP þ CH2Cl2 (688.85): C, 57.49; H, 4.50; N, 2.03. Found:
C, 57.08; H, 5.15; N, 2.02.
97.0 (d, JPC ¼ 1.2 Hz, Cb), 122.4 (d, 1JCF ¼ 319.2 Hz, CF3), 129.4 (d,
3
2JPC ¼ 10.3 Hz, PArC), 131.0 (d, JPC ¼ 2.4 Hz, PArC), 131.8 (PArC),
3
135.1 (Cg), 135.6 (d, 1JPC ¼ 11.2 Hz, PArC), 143.8 (d, JPC ¼ 38.2 Hz,
2
Ca). 31P NMR (161 MHz, CDCl3):
d
¼ 44.8. 19F NMR (376 MHz, CDCl3):
d
¼ ꢀ85.0. UVeVIS lmax (log
3
) [Solv]: 607 nm (3.266) [CH2Cl2]. FAB-
3.17. (h
5-Cyclopentadienyl)(N-ethyl-6-bromo-pyridin-1,2-
propadienylidene)(triphenylphosphine)nickel(II)tetrafluoroborate (11)
MS m/z (%): 530 (12) [Mþ], 515 (24) [(M-CH3)þ], 385 (54) [(M-
C10H8O)þ], 320 (23) [(M-C15H13O)þ]. Anal. Calc. for C34H28F3NiO4PS
(679,31): C, 60.12; H, 4.15. Found: C, 59.99; H, 4.37.
Complex 11 was synthesized from alkynyl complex 9 analo-
gously to the complexes 5ae7a, however, using 1 eq of [Et3O]BF4
instead of [Me3O]BF4. Brown powder. 0.43 g (62%). Mp 53 ꢁC. IR
3.14. (h
5-Cyclopentadienyl)(2-pyridyl-ethynyl)-
(triphenylphosphane)nickel(II) (8)
(CH2Cl2, cmꢀ1):
n
(CCC) ¼ 2070 s. 1H NMR (400 MHz, CDCl3):
3
d
¼ 0.98 (t, JHH ¼ 7.2 Hz, 3H, CH3), 2.14 (q, 2H, NCH2), 5.25 (s, 5H,
Complex 8 was synthesized similar to the complexes 2e4
starting from 2-ethynyl-pyridine and [Cp(Ph3P)NiCl]. Green
powder. Yield: 0.41 g (0.84 mmol, 94%). Mp 73 ꢁC. IR (CH2Cl2, cmꢀ1):
Cp), 6.96, 7.96, 8.50 (3H, Pyr-H), 7.38e7.53 (9H, C6H5), 7.59e7.66
(6H, C6H5). 13C NMR (100 MHz, CDCl3):
d
¼ 15.2 (CH3), 54.4 (NCH2)
93.7 (Cp), 99.7 (d, 3JPC ¼ 1.2 Hz, Cb), 115.9, 131.7, 143.3, 144.7 (4 Pyr-
C), 128.7 (d, 2JPC ¼ 10.7 Hz, P-C6H5), 131.2 (d, 3JPC ¼ 2.4 Hz, P-C6H5),
133.7 (d, 1JPC ¼ 11.3 Hz, P-C6H5), 138.7 (Cg), 152.9 (d, 2JPC ¼ 17.3 Hz,
n
(CC) ¼ 2100 s. 1H NMR (400 MHz, [D6]-acetone):
d
¼ 5.09 (s, 5H,
3
Cp), 6.14 (d, JHH ¼ 7.8 Hz, 1H, Pyr-H), 6.70 (s, 1H, Pyr-H), 7.10 (t,
2JHH ¼ 7.0 Hz, 1H, Pyr-H), 7.31e7.39 (m, 9H, C6H5), 7.61e7.84 (m, 6H,
Ca). 31P NMR (161 MHz, CDCl3):
d
¼ 43.1. 19F NMR (376 MHz, CDCl3):
C6H5), 8.07 (s, 1H, Pyr-H). 13C NMR (100 MHz, CDCl3):
d
¼ 93.2 (d,
d
¼ ꢀ153.2. UVeVIS lmax (log
3) [Solv]: 485 nm (3.694) [CH2Cl2].
2JPC ¼ 39.3 Hz, Ca), 94.0 (d, 2JPC ¼ 1.6 Hz, Cp), 113.4 (d, 3JPC ¼ 1.2 Hz,
Cb),120.7,135.9,136.0,148.3 (4 Pyr-C),129.7 (d, 2JPC ¼ 10.4 Hz, C6H5),
131.2 (s, C6H5), 131.8 (d, 3JPC ¼ 1.6 Hz, C6H5), 135.4 (d, 1JPC ¼ 10.4 Hz,
FAB-MS m/z (%): 597 (57) [Mþ], 385 (16) [(M-C9H8BrN)þ], 320 (14)
[(M-C9H8BrN-C5H5)þ], 263 (9) [(M-C9H8BrN-C5H5-Ni)þ]. Anal. Calc.
for C32H28BBrF4NNiP (682.95): C, 56.28; H, 4.13; N, 2.05. Found: C,
56.27; H, 4.32; N, 1.85.
C6H5), 150.1 (Cg). 31P NMR (161 MHz, CDCl3):
d
¼ 42.5. UVeVIS lmax
(log 3) [Solv]: 413 nm (3.091) [CH2Cl2]. FAB-MS m/z (%): 488 (47)
[Mþ], 385 (21) [(M-2H-C7H4N)þ], 320 (15) [(M-2H-C7H4N-C5H5)þ],
263 (38) [(Ph3P)]. Anal. Calc. for C30H24NNiP (488.19): C, 73.68; H,
4.96; N, 2.87. Found: C, 73.27; H, 4.87; N, 2.95.
3.18. h
5-Cyclopentadienyl(N-trifluoroboryl-2-pyridyl-ethynyl)-
(triphenylphosphane)nickel(II) (12)
To a solution of complex 8 (1 mmol) in 50 ml of Et2O 0.2 ml of
BF3ꢂEt2O was added while stirring. An orange precipitate formed
that was filtered off and washed with 50 ml of Et2O. Drying of the
precipitate under vacuum gave a brown powder that decomposed
3.15.
h
5-Cyclopentadienyl(2-{5-bromopyridyl}ethynyl)-
(triphenylphosphane)nickel(II) (9)
Complex 9 was synthesized similar to the complexes 2e4
starting from 2-ethynyl-5-bromo-pyridine and [Cp(Ph3P)NiCl].
Brown powder. Yield: 0.39 g (70 mmol, 70%). Mp 65 ꢁC (dec.). IR
quickly when exposed to air. Yield: 0.30 g (54%). IR (CH2Cl2, cmꢀ1):
n
(CC) ¼ 2069 vs. 1H NMR (400 MHz, CDCl3):
¼ 5.27 (s, 5H, Cp), 6.34
d
(d, 3JHH ¼ 8.3 Hz, 1H, Py), 6.97 (t, 1H, Py), 7.36e7.64 (m, 15H, C6H5),
(CH2Cl2, cmꢀ1):
n
(CC) ¼ 2101 s. 1H NMR (400 MHz, [D6]-acetone):
7.75 (t, 3JHH ¼ 8.6 Hz,1H, Py), 8.35 (d, 3JHH ¼ 8.2 Hz,1H, Py). 13C NMR
3
d
¼ 5.14 (s, 5H, Cp), 6.0 (d, JHH ¼ 8.4 Hz, 1H, Pyr-H), 7.19 (dd,
(100 MHz, CDCl3):
d
¼ 77.2 (Cp), 93.5 (Ca), 109.9 (Cb), 117.9, 122.6,
3JHH ¼ 8.4 Hz, JHH ¼ 2.4 Hz, 1H, Pyr-H), 7.27e7.36 (m, 9H, C6H5),
129,4, 133.5, 133.7 (Py), 134.2e139.2 (C6H5), 173.9 (Cg). 31P NMR
4