Organometallics
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[Pd(CH3)(NCCH3)(4)][PF6] (4a). Pale yellow solid (yield 57%). IR
(KBr): 1733 cm−1 ν(COO−). MALDI-TOF: calcd for
2H, (CH)3,3′), 8.71 (dd, 1H, (CH)4′, 3JH4′‑H3′ = 8.5 Hz, 4JH4′‑H6′ = 1 Hz),
3
4
8.75 (dd, 1H, (CH)4, JH4−H3 = 8.5 Hz, JH4−H6 = 1 Hz), 9.07 (s, 1H,
(CH)6′), 9.18 (s, 1H, (CH)6). 19F NMR (376.3 MHz, CD2Cl2): δ
−63.3 (CF3, BARF), −81.6 (CF3), −114.9 (CF2), −122.4 (CF2),
−122.6 (CF2), −123.4 (CF2), −124.1 (CF2), −126.8 (CF2). 15N
NMR (40 MHz, CD2Cl2): δ −204.8 (NCCH3), −155.9 (Ncis), −118.2
(Ntrans).
(C37H24F40N3O4PPd) m/z 1419.9080 [M+ − CH3 − PF6 + Ag+],
−
1473.0066 [M+ + 2H+]; found m/z 1419.1599 [M+ − CH3 − PF6
+
−
Ag+], 1472.9887 [M+ + 2H+]. H NMR (500 MHz, CD2Cl2): δ 1.25
(s, 3H, Pd-CH3), 2.18 (m, 4H, (CH2)2″), 2.32 (m, 4H, (CH2)3″), 2.55
(s, 3H, Pd-NCCH3), 4.53 (t, 4H, (CH2)1″, J = 6.25 Hz), 8.45 (pst, 2H,
(CH)3,3′), 8.77 (pst, 2H, (CH)4,4′), 9.08 (s, 1H, (CH)6′), 9.15 (s, 1H,
(CH)6). 19F NMR (376.3 MHz, CD2Cl2): δ −73.1 (PF6, JP−F = 712
Hz), −81.1 (CF3), −114.5 (CF2), −121.9 (CF2), −122.1 (CF2),
−122.9 (CF2), −123.5 (CF2), 126.3 (CF2). 15N NMR (40 MHz,
CD2Cl2): δ −205.6 (NCCH3), −156.6 (Ncis), −119.0 (Ntrans).
1
[Pd(N−N)2][BArF]2 (1d−4d). To a suspension of [PdCl2(N−N)]
(0.072 mmol) in 20 mL of dichloromethane was slowly added a
solution of the ligand 1−4 (0.076 mmol) and sodium tetrakis(3,5-
(trifluoromethyl)phenyl)borate (128.4 mg, 0.145 mmol) in 10 mL of
dichloromethane. The mixture was heated for 1 h at 40 °C. The
product was filtered off over Celite, and the solvent was removed
under reduced pressure. The product obtained as an oil was triturated
in pentane, and a solid was obtained.
[Pd(CH3)(NCCH3)(4)][OTs] (4b). Brownish-green powder (yield
52%). IR (KBr): 1730 cm−1 ν(COO−). MALDI-TOF: calcd for
(C44H31F34N3O7PdS) m/z 1419.9080 [M+ − CH3 − OTs− + Ag+],
1474.0462 [M+ − NCCH3 + NH4 ]; found m/z 1419.1079 [M+ −
+
1
[Pd(1)2][BArF]2 (1d). Pale yellow solid (yield 34%). H NMR (400
CH3 − OTs− + Ag+], 1474.2297 [M+ − NCCH3 + NH4 ]. H NMR
(500 MHz, CD2Cl2): δ 1.15 (s, 3H, Pd-CH3), 1.27 (s, 3H, CH3-OTs),
2.16 (m, 4H, (CH2)3″), 2.31 (m, 4H, (CH2)2″), 2.39 (s, 3H, CH3CN-
+
1
MHz, (CD3)2CO): δ 1.77 (m, 8H; (CH2)−4″), 2.04 (m, 8H; (CH2)3″),
2.32 (m, 8H, (CH2)2″), 3.14 (t, 8H, (CH2)1″, J = 7.2 Hz); 7.66 (s,
8Hpara, BArF), 7.79 (d, 16Hortho, BArF), 8.04 (d, 4H, H5,5′), 8.82 (s, 4H,
H3,3′), 9.18 (d, 4H, H6,6′, J = 5.6 Hz); 19F NMR (376.3 MHz,
(CD3)2CO): δ −63.7 (CF3, BArF), −81.2 (CF3), −114.2 (CF2),
−122.4 (CF2), −123.2 (CF2), 0.123.9 (CF2), −126.6 (CF2). EIMS:
m/z calcd for C132H68B2F116N4Pd 2314.1 [M − 2BArF]; found 2314.4.
3
Pd), 4.51 (psq, 4H, (CH2)1″), 7.24 (d, 2H, m-CH-OTs, JHm‑Ho = 9
3
Hz), 7.81 (d, 2H, o-CH-OTs, JHo‑Hm = 9 Hz), 8.26 (d, 1H, (CH)3,
3
3JH3−H4 = 8.5 Hz), 8.30 (d, 1H, (CH)3′, JH3′‑H4′ = 8.5 Hz), 8.67 (m,
4
2H, (CH)4,4′), 9.18 (d, 1H, (CH)6, JH6−H4 = 2 Hz), 9.71 (d, 1H,
1
4
(CH)6′, JH6′‑H4′ = 2 Hz). 19F NMR (376.3 MHz, CD2Cl2): δ −81.5
[Pd(2)2][BArF]2 (2d). Pale brown solid (yield 53%). H NMR (400
MHz, CD2Cl2): δ 1.63 (4H, m, (CH2)2″), 1.71 (4H, m, (CH2)3″), 2.13
(4H, m, (CH2)4″), 2.40 (6H, s, CH3), 2.72 (4H, m, (CH2)1″), 7.64
(1H, d, CH4′, J = 8.1 Hz), 7.65 (1H, d, CH4, J = 8.1 Hz), 8.24 (1H, d,
CH3′, J = 8.1 Hz), 8.28 (1H, d, CH3, J = 8.1 Hz), 8.51 (2H, s, CH6,6′),
7.55 (s, 8Hpara, BArF), 7.73 (d, 16Hortho, BArF); 19F NMR (376.3
MHz, DMSO-d): δ −126.2 (CF2), −123.5 (CF2), −122.9 (CF2),
−122.2 (CF2), −113.7 (CF2), −80.7 (CF3), −62.0 (CF3, BArF).
MALDI-TOF: m/z calcd for C110H58B2F82N4Pd 1397.1521 [M −
2BArF]; found 1397.3773.
(CF3), −115.0 (CF2), −122.4 (CF2), −122.5 (CF2), −123.3 (CF2),
−123.7 (CF2), −126.8 (CF2). 15N NMR (40 MHz, CD2Cl2): δ
−135.0 (Ntrans).
[Pd(CH3)(NCCH3)(N−N)][BArF] (2c−4c). Two drops of dry aceto-
nitrile were added to a suspension of 2b−4b (3.4 × 10−2 mmol) and
1.1 equiv of NaBArF (33 mg, 3.7 × 10−2 mmol) dissolved in dry
CH2Cl2 (2 mL). The mixture was stirred for 0.5 h at 0 °C and then for
1 h at room temperature. The resulting suspension was filtered off to
remove the precipitated NaOTs, which was washed with dry
dichloromethane. The filtrate was evaporated under vacuum to yield
an oil, which was triturated with pentane, yielding a foam.
[Pd(CH3)(NCCH3)(2)][BArF] (2c). Pale brown foam (yield 97%).
1
[Pd(3)2][BArF]2 (3d). Pale brown solid (yield 92%). H NMR (400
MHz, 298 K, CDCl3): ratio I:II = 1:1; δ (ppm) 2.17 (16H, m,
(CH2)2″,3″, I and II), 4.51 (4H, t, (CH2)1″, J = 6.4 Hz, II), 4.57 (4H, t,
(CH2)1″, J = 6.2 Hz, I), 8.03 (2H, dd, CH5, J = 5.6 Hz, J = 1.6 Hz, II),
7.46 (16H, br, Hpara BArF), 7.66 (32H, br, Hortho BArF), 8.20 (2H, dd,
CH5, J = 5.2 Hz, J = 1.6 Hz, I), 8.52 (2H, d, CH6, J = 5.2 Hz, I), 8.70
(2H, d, CH3, J = 1.6 Hz, II), 8.77 (2H, d, CH6, J = 5.6 Hz, II), 8.77
(2H, s, CH3, I); 19F NMR (376.3 MHz, CDCl3): δ (ppm) −127.5
(CF2′), −126.7 (CF2), −124.6 (CF2′), −123.9 (CF2), −123.2 (CF2),
−123.2 (CF2′), −122.5 (CF2′), −122.2 (CF2), −115.5 (CF2′), −114.8
(CF2), −82.4 (CF3′), −81.2 (CF3), −63.4 (CF3′, BArF), −62.9 (CF3,
BArF). MALDI-TOF: m/z calcd for C132H60B2F116N4O8Pd 2434.0499
[M − 2BArF]; found 2434.2235. IR: ν(COO) 1742 and 1713 cm−1.
MALDI-TOF: calcd for (C58H35BF41N3Pd) m/z 1600.1373 [M+
−
CF3], 1643.1613 [M+ − CF3 + Na+ + NH4 ]; found m/z 1599.1922
+
[M+ − CF3], 1643.1685 [M+ − CF3 + Na+ + NH4 ]. H NMR (400
MHz, CD2Cl2): δ 1.09 (s, 3H, Pd-CH3), 1.71 (m, 2H, (CH2)2″), 1.78
(m, 2H, (CH2)3″), 2.16 (m, 2H, (CH2)4″), 2.48 (s, 3H, Pd-NCCH3),
2.55 (d, 3H, (CH3)1‴), 2.81 (m, 2H, (CH2)1″), 7.54 (s, 4H, BArF),
7.71 (s, 8H, BArF), 7.90−8.10 (m, 4H, (CH)4,4′, (CH)3,3′), 8.23 (d,
1H, (CH)6), 8.33 (s, 1H, (CH)6′). 19F NMR (376.3 MHz, CD2Cl2): δ
−63.3 (CF3, BARF), −81.5 (CF3), −115.1 (CF2), −122.4 (CF2),
−122.6 (CF2), −123.4 (CF2), −124.2 (CF2), −126.8 (CF2). 15N
NMR (40 MHz, CD2Cl2): δ −165.9 (Ncis).
+
1
1
[Pd(4)2][BArF]2 (4d). Pale brown solid (yield 61%). H NMR (400
MHz, 298 K, CDCl3): ratio I:II = 1:1; δ (ppm) 2.08 (16H, m,
(CH2)2″,3″ I and II), 2.25 (16H, m, (CH2)2″‑3″ 4.42 (8H, t, (CH2)1″, J =
6.2 Hz, II), 4.52 (8H, t, (CH2)1″, J = 9.6 Hz, II) 7.48 (16H, br, Hpara
BArF), 7.68 (32H, br, Hortho BArF), 7.82 (2H, d, CH3, J = 8 Hz, II),
7.96 (2H, m, CH3, I), 8.52 (4H, d, CH4, J = 8 Hz, II), 8.63 (4H, d,
CH4, J = 8 Hz, I), 9.15 (4H, s, CH6, II) 9.20 (4H, s, CH6, I). 19F NMR
(376.3 MHz, CDCl3): δ (ppm) −126.7 (CF2), −123.9 (CF2), −123.3
(CF2), −122.5 (CF2), −122.3 (CF2), −114.9 (CF2), −81.3 (CF3),
−62.9 (CF3 , BArF). MALDI-TOF: m/z calcd for
[Pd(CH3)(NCCH3)(3)][BArF] (3c). Brownish-yellow foam (Yield
65%). IR (KBr): 1744 cm−1 ν(COO). MALDI-TOF: calcd for
(C69H36BF58N3O4Pd) m/z 1393.9049 [M+ − NCCH3 − BArF + Ag+],
1419.9080 [M+ − CH3 − BArF + Ag+]; found m/z 1393.0875 [M+ −
1
NCCH3 − BArF + Ag+], 1419.1705 [M+ − CH3 − BArF + Ag+]. H
NMR (500 MHz, CD2Cl2): δ 1.23 (s, 3H, Pd-CH3), 2.20 (m, 4H,
(CH2)2″), 2.30 (m, 4H, (CH2)3″), 2.52 (s, 3H, Pd-NCCH3), 4.56 (t,
3
4H, (CH2)1″, JH−H = 6 Hz), 7.55 (s, 4H, BArF), 7.71 (s, 8H, BArF),
3
4
8.18 (dd, 1H, (CH)5, JH5−H6 = 5.5 Hz, JH5−H3 = 1 Hz), 8.21 (d, 1H,
(CH)5′, 3JH5′‑H6′ = 3.5 Hz), 8.66 (d, 1H, (CH)6, 3JH6−H5 = 5.5 Hz), 8.76
C
132H60B2F116N4O8Pd 2434.0499 [M − 2BArF]; found 2434.2408.
IR: ν(COO) 1741 cm−1.
(d, 1H, (CH)6′, JH6′‑H5′ = 5.5 Hz), 8.82 (s, 2H, (CH)3′,3). 19F NMR
3
[Pd(N−N)2][X]2 (1d−1d″). To a suspension of [PdCl2(N−N)]
(0.030 mmol) in 10 mL of dichloromethane was slowly added a
solution of the ligand 1 (0.0318 mmol) and the corresponding silver
salt (0.0618 mmol) in 5 mL of dichloromethane. The mixture was
heated for 1 h at 40 °C. The product was filtered off over Celite, and
the solvent was removed under reduced pressure. The product
obtained as an oil was triturated in pentane, and pale yellow solids
were formed.
(376.3 MHz, CD2Cl2): δ −63.3 (CF3, BArF), −81.6 (CF3), −114.9
(CF2), −122.4 (CF2), −122.6 (CF2), −123.4 (CF2), −124.1 (CF2),
−126.8 (CF2). 15N NMR (40 MHz, CD2Cl2): δ −204.3 (NCCH3),
−149.3 (Ncis), −111.5 (Ntrans).
[Pd(CH3)(NCCH3)(4)][BArF] (4c). Pale brown foam (yield 47%). IR
(KBr): 1741 cm−1 ν(COO). MALDI-TOF: calcd for
(C69H36BF58N3O4Pd) m/z 1419.9080 [M+ − CH3 − BArF + Ag+],
1477.9755 [M+ − BArF + CF3COO− + K+]; found m/z 1419.0966
[M+ − CH3 − BArF + Ag+], 1477.1439 [M+ − BArF + CF3COO− +
1
[Pd(1)2][PF6]2 (1d′). Pale yellow solid (yield 30%). H NMR (400
K+]. H NMR (400 MHz, CDCl3): δ 1.27 (s, 3H, Pd-CH3), 2.18 (m,
MHz, CDCl3): δ 1.70 (m, 8H; (CH2)−4″), 1.81 (m, 8H; (CH2)3″), 2.10
(m, 8H, (CH2)2″), 2.76 (t, 8H, (CH2)1″, J = 7.2 Hz); 7.16 (d, 4H,
H5,5′), 8.26 (s, 4H, H3,3′), 8.59 (d, 4H, H6,6′, J = 4.4 Hz). 19F NMR
1
4H, (CH2)2″), 2.30 (m, 4H, (CH2)3″), 2.53 (s, 3H, Pd-NCCH3), 4.52
(psq, 4H, (CH2)1″), 7.55 (s, 4H, BArF), 7.71 (s, 8H, BArF), 8.30 (pst,
6584
dx.doi.org/10.1021/om200642s | Organometallics 2011, 30, 6572−6586