5220 Organometallics, Vol. 28, No. 17, 2009
Hussain et al.
The color of the reaction mixture became violet brown. After
stirring the mixture for 14 h the solvent was removed at reduced
pressure. The crude product was extracted with diethyl ether
(3ꢀ25 mL) and was chromatographed (30ꢀ4 cm, petroleum
ether/ethyl acetate, 10:1) to yield 0.09 g (0.2 mmol, 67%) of 16 as
a deep brown solid (mp 109 °C, dec). IR (ATR): ~ν 3051 (w), 2958
(w), 2899 (w), 2869 (w), 2168 (w), 2085 (m, CC), 1471 (m), 1429
(m), 1259 (s), 1124 (s), 1079 (s), 1014 (s), 845 (w), 790 (s), 750 (m),
82%) of 18 as a red-brown solid (mp 122 °C, dec). IR (ATR): ν~
3278 (w), 2943 (m), 2895 (w), 2861 (w), 1946 (s, CC), 1467 (m),
1389 (m), 1366 (w), 1321 (w), 1260 (w), 1183 (m), 1128 (w), 1110
(w), 1012 (m), 933 (w), 923 (w), 822 (m), 802 (s), 742 (s) cm-1. 1H
NMR (CDCl3, 400 MHz): δ 1.18 (d, 3JPH=13.4 Hz, 9H, CH3),
1.39 (d, 3JPH=13.2 Hz, 9H, CH3), 1.61 (d, J=1.6 Hz, 1H, CCH),
2.15-2.50 (m, 2H, PCH2CH2), 2.64-2.88 (m, 2H, PCH2), 5.58
(dd, 3JHH=4.1, 3.3 Hz, 1H, 3-H), 6.39 (d, 3JHH=3.0 Hz, 1H, 2-
H), 6.98-7.00 (m, 1H, 5-H), 7.02-7.11 (m, 2H, 4-H, 7-H),
7.19-7.21 (m, 1H, 6-H) ppm. 13C NMR (CDCl3, 100 MHz, BB):
δ 25.5 (d, 2JCP=5.0 Hz, PCH2CH2), 29.2 (d, 2JCP=3.5 Hz, CH3),
29.7 (d, 2JCP=3.6 Hz, CH3), 35.4 [d, 1JCP=14.6 Hz, C(CH3)3],
1
730 (s), 697 (s) cm-1. H NMR (CDCl3, 400 MHz): δ 1.20 (d,
3
3JPH=13.6 Hz, 9H, CH3), 1.40 (d, JPH=13.1 Hz, 9H, CH3),
2.19-2.47 (m, 4H, PCH2CH2), 5.63 (dd, 3JHH=3.1, 1.2 Hz, 1H,
3-H), 6.44 (d, 3JHH=3.1 Hz, 1H, 2-H), 6.95-7.02 (m, 2H, 5-H,
p-H), 7.06-7.12 (m, 3H, 4-H, m-H), 7.14-7.16 [m, 2H, 6-H, 7-
H), 7.23 (d, 3JHH=7.6 Hz, 2H, o-H) ppm. 13C NMR (CDCl3,
1
1
36.0 [d, JCP = 14.8 Hz, C(CH3)3], 38.8 (d, JCP = 18.6 Hz,
PCH2), 74.8 (d, JCP =11.9 Hz, C-3), 93.2 (d, JCP =25.3 Hz,
2
2
3
NiCC), 98.7 (d, JCP = 8.1 Hz, C-1), 102.8 (d, JCP = 1.3 Hz,
100 MHz, BB): δ 25.6 (d, JCP =4.6 Hz, PCH2CH2), 29.2 (d,
=
2JCP=3.4 Hz, CH3), 29.7 (d, 2JCP=3.6 Hz, CH3), 35.4 [d, 1JCP
NiCC), 104.2 (d, JCP=2.1 Hz, C-2), 117.3 (s, C-7), 119.3 (s, C-6),
123.3 (s, C-5), 124.4 (s, 3a), 125.5 (d, JCP=1.3 Hz, C-7a), 126.0
(s, C-4). 31P NMR (CDCl3, 161 MHz): δ 95.7 (s) ppm. MS (70
eV): m/z (%) 370 (57) [Mþ], 313 (14) [Mþ - C4H9], 288 (22) [Mþ
- C4H9 - C2H], 257 (39) [Mþ - C4H9 - C4H8], 232 (14), 186
(43) [Mþ - C11H21P], 173 (22), 141 (47), 128 (34), 115 (40), 104
(10). HRMS: calcd for C21H29NiP 370.1360; found 370.1360.
Anal. Calcd for C21H29NiP (370.1): 67.96, H 7.88. Found: C
68.18, H 7.88.
1
14.4 Hz, C(CH3)3], 36.0 [d, JCP=14.6 Hz, C(CH3)3], 38.9 (d,
1JCP =18.1 Hz, PCH2), 74.5 (d, JCP =12.2 Hz, C-3), 97.6 (d,
3
2JCP=26.9 Hz, NiCC), 98.7 (d, JCP=7.2 Hz, C-1), 104.4 (d,
JCP=2.2 Hz, C-2), 117.2 (s, C-7), 117.4 (s, NiCC), 119.4 (s, C-6),
123.2 (s, C-5), 124.4 (s, p-CH), 124.7 (s, C-3a), 125.8 (s, C-4),
125.9 (d, JCP=1.5 Hz, C-7a) 127.6 [s, ImI-CH], 128.8 (d, 4JCP
=
1.0 Hz, 13a-C), 131.2 [d, 5JCP=0.7 Hz, o-CH] ppm. 31P NMR
(CDCl3, 161 MHz): δ 95.6 (s) ppm. MS (ESI acetonitrile): m/z
(%) 716 (14) [Mþ - C4H8 þ C19H28P þ K], 460 (28) [Mþ þ H -
C2H4 þ CH3CN], 447 (13) [Mþ þ H], 435 (4) [Mþ - C4H4 þ Na
{[1-(Di-tert-butylphosphanylethyl)indenyl][2-(2-pyridyl)ethy-
nyl)}nickel(II) (19). 2-Ethynylpyridine (0.25 g, 2.2 mmol) was
added dropwise to a suspension of 8 (0.76 g, 2.0 mmol) and CuI
(5 mg, 0.03 mmol) in freshly distilled triethylamine (25 mL). The
color of the reaction mixture became brown. After stirring the
mixture for 4 h the solvent was removed at reduced pressure. The
crude product was extracted with diethyl ether (3ꢀ50 mL) and
chromatographed (15ꢀ3 cm, petroleum ether/diethyl ether, 6:1)
to yield 0.60 g (1.3 mmol, 67%) of 19 as an orange-brown solid
(mp 148 °C, dec). IR (ATR): ν~ 3156 (w), 2945 (m), 2896 (w), 2860
(w), 2083 (s, CC), 1580 (s), 1551 (m), 1456 (s), 1419 (m), 1390
(m), 1367 (w), 1322 (w), 1236 (m), 1175 (m), 1147 (w), 1129 (w),
1015 (m), 933 (w), 923 (w), 823 (w), 811 (m), 776 (s), 737 (s), 675
(m) cm-1. 1H NMR (CDCl3, 400 MHz): δ 1.18 (d, 3JPH=13.7
Hz, 9H, CH3), 1.41 (d, 3JPH=13.1 Hz, 9H, CH3), 2.15-2.24 (m,
1H, PCH2CH2), 2.36-2.52 (m, 1H, PCH2CH2), 2.66-2.74 (m,
1H, PCH2), 2.80-2.91 (m, 1H, PCH2), 5.65 (dd, 3JHH=4.2, 3.3
þ H2O], 386 (100) [Mþ - C8H5 þ CH3CN], 372 (62) [Mþ
-
C8H17], 352 (12) [Mþ - C12H14 þ CH3CN þ Na], 336 (9) [Mþ -
C10H8 þ H2O], 319 (6) [Mþ - C14H23 þ CH3CN þ Na], 303 (12)
[C19H28PO]. HRMS (ESI acetonitrile): calcd for C27H33NiP
[Mþ þ H] 447.1752; found 447.1751.
{[1-(Di-tert-butylphosphanylethyl)indenyl](2-trimethylsilyl-
ethynyl)}nickel(II) (17). Ethynyltrimethylsilane (180 mg, 1.8
mmol) was added dropwise to a suspension of 8 (380 mg, 1.0
mmol) and CuI (5 mg, 0.03 mmol) in freshly distilled triethyla-
mine (5 mL). The color of the reaction mixture became brown.
After stirring the mixture for 14 h the solvent was removed at
reduced pressure. The crude product was extracted with diethyl
ether (2 ꢀ 30 mL) and was chromatographed (20 ꢀ 3 cm,
petroleum ether/diethyl ether, 9:1) to yield 270 mg (0.6 mmol,
60%) of 17 as a green solid (mp 141 °C, dec). IR (ATR): ν~ 2948
(w), 2897 (w), 2864 (w), 2022 (s, CC), 1737 (w), 1737 (w), 1474
(m), 1390 (m), 1367 (w), 1324 (w), 1237 (m), 1182 (m), 1128 (w),
Hz, 1H, 3-H), 6.40 (d, 3JHH=3.1 Hz, 1H, 2-H), 6.84 (ddd, 3JHH
7.4, 4.9, 1.2 Hz, 1H, NCCH), 6.97-7.01 (m, 2H, 5-H,
=
1016 (m), 857 (s), 832 (s), 811 (s), 752 (s), 733 (m), 684 (s) cm-1
.
NCCHCH), 7.08-7.11 (m, 2H, 4-H, 6-H), 7.24 (dd, JH,H =
3
1H NMR (CDCl3, 400 MHz): δ -0.05 [s, 9H, Si(CH3)3], 1.17 (d,
3JPH=13.6 Hz, 9H, CCH3), 1.37 (d, 3JPH=13.4 Hz, 9H, CCH3),
2.15-2.19 (m, 1H, PCH2CH2), 2.38-2.43 (m, 1H, PCH2CH2),
2.64-2.71 (m, 1H, PCH2), 2.79-2.84 (m, 1H, PCH2), 5.57 (d,
3JHH=3.9 Hz, 1H, 3-H), 6.37 (d, 3JHH=3.1 Hz, 1H, 2-H), 6.98
(t, 3JHH=7.5 Hz, 1H, 5-H), 7.06-7.12 (m, 2H, 4-H, 7-H), 7.21
(d, 3JHH=7.8 Hz, 1H, 6-H) ppm. 13C NMR (CDCl3, 100 MHz,
BB): δ 1.31 [s, Si(CH3)3], 25.3 (d, 2JCP=4.8 Hz, PCH2CH2), 29.1
7.9, 0.6 Hz, 1H, 7-H), 7.35 (dt, JH,H = 7.6, 1.9 Hz, 1H,
NCHCH), 8.34 (ddd, 3JH,H=4.9, 1.8, 0.8 Hz, 1H, NCH) ppm.
3
2
13C NMR (CDCl3, 100 MHz, BB): δ 25.5 (d, JCP =4.8 Hz,
PCH2CH2), 29.2 (d, 2JCP=3.4 Hz, CH3), 29.7 (d, 2JCP=3.7 Hz,
CH3), 35.4 [d, 1JCP=14.8 Hz, C(CH3)3], 36.0 [d, 1JCP=15.0 Hz,
C(CH3)3], 38.8 (d, JCP=18.6 Hz, PCH2), 74.9 (d, JCP=11.9
1
Hz, C-3), 99.3 (d, 3JCP=8.2 Hz, C-1), 104.4 (d, JCP=2.2 Hz, C-
2
2), 105.0 (d, JCP =26.2 Hz, NiCC), 117.2 (s, C-6), 118.5 (d,
2
2
(d, JCP=3.4 Hz, CH3), 29.6 (d, JCP=3.6 Hz, CH3), 35.2 [d,
3JCP = 1.6 Hz, NiCC), 119.3 (s, NCCH), 119.7 (s, C-7), 123.4 (s,
C-5), 124.3 (s, C-3a), 125.5 (d, JCP=1.6 Hz, C-7a), 125.9 (s, C-4),
126.1 (s, NCCHCH), 135.2 (s, NCHCH), 146.6 (d, JCP=1.0 Hz,
NiCCC), 149.2 (s, NCH) ppm. 31P NMR (CDCl3, 161 MHz): δ
96.3 (s) ppm. MS (70 eV): m/z (%) 447 (66) [Mþ], 391 (13) [Mþ -
C4H9], 334 (82) [Mþ - C4H9 - C4H8], 288 (31) [Mþ - C4H8 -
C4H4N - C2H], 232 (12), 207 (16), 192 (30), 173 (20), 141 (36),
128 (25), 115 (27), 103 (51), 76 (25), 57 (100). HRMS: calcd for
C26H32NNiP 447.1626; found 447.1627. Anal. Calcd for
C26H32NNiP (447.2): C 69.67, H 7.20, N 3.13. Found: C
69.18, H 7.34, N 3.29.
1JCP=14.6 Hz, C(CH3)3], 35.9 [d, JCP = 14.6 Hz, C(CH3)3],
1
38.8 (d, 1JCP=18.2 Hz, PCH2), 74.1 (d, JCP v 12.1 Hz, C-3), 98.7
(d, 3JCP=8.1 Hz, C-1), 104.4 (d, JCP=2.3 Hz, C-2), 117.0 (s, C-
7), 119.4 (s, C-6), 122.2 (d, 2JCP=25.3 Hz, NiCC), 123.0 (s, C-5),
124.6 (s, NiCC), 125.4 (s, C-4), 125.6 (d, JCP=1.3 Hz, C-3a),
125.6 (d, JCP =1.5 Hz, C-7a). 31P NMR (CDCl3, 161 MHz):
δ 94.8 (s) ppm. MS (70 eV): m/z (%) 442 (100) [Mþ], 385 (19)
[Mþ - C4H9], 329 (13) [Mþ - 2 C4H9], 231 (15) [Mþ - 2 C4H9 -
Si(CH3)3 - C2], 186 (24) [Mþ - C14H29PSi], 128 (24), 106 (14),
83 (10), 57 (60). HRMS: calcd for C24H37NiPSi 442.1756; found
442.1753.
{[1-(Di-tert-butylphosphanylethyl)indenyl][2-(2-methoxy-2-
oxoethyl)pyridiniumethynyl]}nickel(II) Bromide (20). Methyl-
bromoacetate (1 mL, 0.1 mmol) was added dropwise to a
suspension of 19 (0.05 g, 0.1 mmol) in diethyl ether (25 mL).
The color of the reaction mixture became red. After stirring the
mixture for 12 h the solvent was removed at reduced pressure.
The crude product was washed with hexane (5 ꢀ 25 mL) to yield
[1-(Di-tert-butylphosphanylethyl)indenyl](ethynyl)nickel(II)
(18). Potassium carbonate (0.17 g, 1.2 mmol) was added to a
solution of 17 (0.18 g, 0.4 mmol) in methanol (20 mL). After
stirring the solution for 2 h the solvent was removed at reduced
pressure. The crude product was chromatographed (10 ꢀ 1 cm,
petroleum ether/diethyl ether, 3:1) to yield 0.12 g (0.3 mmol,