Transition Met Chem (2016) 41:403–411
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163.7, 154.3, 141.5, 139.2, 138.5, 127.2, 126.9, 112.8,
109.3, 65.1, 53.3.
2-(2-Pyrazinyl)phenylmethanol 7g. Anal. Calcd. for
C11H10N2O: C, 70.9; H, 5.4; N, 15.0. Found: C, 71.3; H,
5.2; N, 15.3 %. MS–ESI? [m/z]: 187.1 (M ? H)?. 1H
NMR (400 MHz, CDCl3): d 9.97 (d, J = 1.0 Hz, 1H), 8.56
(d, J = 1.0 Hz, 2H), 7.62 (d, J = 6.4 Hz, 1H), 7.56 (d,
J = 6.0 Hz, 1H), 7.50–7.53 (m, 2H), 5.25 (br, 1H), 4.51 (s,
2H). 13C NMR (100 MHz, CDCl3): 154.4, 145.2, 143.2,
142.4, 140.7, 136.3, 131.6, 130.3, 129.7, 128.1, 127.6,
64.3.
4-(5-Acetyl-2-pyridinyl)phenylmethanol 6f. Anal. Calcd.
for C14H13NO2: C, 74.0; H, 5.8; N, 6.2. Found: C, 74.3; H,
1
5.5; N, 6.6 %. MS–ESI? [m/z]: 228.1 (M ? H)?. H NMR
(400 MHz, CDCl3): d 9.22 (d, J = 1.2 Hz, 1H), 8.30 (d,
J = 6.4 Hz, 1H), 8.05 (d, J = 6.4 Hz, 2H), 7.85 (d,
J = 6.8 Hz, 1H), 7.50 (d, J = 6.4 Hz, 2H), 4.79 (s, 2H),
2.68 (s, 3H), 2.29 (br, 1H). 13C NMR (100 MHz, CDCl3):
196.6, 160.7, 150.1, 143.1, 137.3, 136.5, 130.6, 127.6, 127.3,
120.2, 64.8, 26.8.
2-(2-Pyrimidinyl)phenylmethanol 7h. Anal. Calcd. for
C11H10N2O: C, 70.9; H, 5.4; N, 15.0. Found: C, 71.2; H,
5.1; N, 15.3 %. MS–ESI? [m/z]: 187.1 (M ? H)?. 1H
NMR (400 MHz, CDCl3): d 8.90 (d, J = 4.0 Hz, 2H),
8.20–8.23 (m, 1H), 7.50–7.53 (m, 3H), 7.32–7.35 (m, 1H),
5.92 (br, 1H), 4.62 (s, 2H). 13C NMR (100 MHz, CDCl3):
156.1, 157.1, 140.7, 137.5, 131.5, 131.3, 130.9, 128.3,
119.0, 64.8.
2-(5-Methyl-2-pyridinyl)phenylmethanol 7b. Anal. Calcd.
for C13H13NO: C, 78.4; H, 6.6; N, 7.0. Found: C, 78.8; H, 6.3;
N, 7.2 %. MS–ESI? [m/z]: 200.1 (M ? H)?. 1H NMR
(400 MHz, CDCl3): d 8.48 (s, 1H), 7.66 (d, J = 6.0 Hz, 1H),
7.42–7.53 (m, 5H), 6.52 (br, 1H), 4.48 (s, 2H), 2.42 (s, 3H).
13C NMR (100 MHz, CDCl3): 156.4, 148.4, 140.3, 139.9,
138.2, 131.9, 131.1, 129.9, 128.1, 123.7, 121.7, 64.7, 18.2.
2-(6-Methyl-2-pyridinyl)phenylmethanol 7c. Anal. Calcd.
for C13H13NO: C, 78.4; H, 6.6; N, 7.0. Found: C, 78.7; H,
Crystal structure determination
1
6.2; N, 7.3 %. MS–ESI? [m/z]: 200.1 (M ? H)?. H NMR
Crystallographic data for complexes 2 and 3 were collected
on an Xcalibur Eos Gemini diffractometer with Cu–Ka
(400 MHz, CDCl3): d 7.76 (t, J = 6.0 Hz, 1H), 7.55–7.59
(m, 1H), 7.51–7.54 (m, 1H), 7.44–7.49 (m, 3H), 7.21 (d,
J = 6.4 Hz, 1H), 6.64 (br, 1H), 4.49 (s, 2H), 2.65 (s, 3H).
13C NMR (100 MHz, CDCl3): 158.6, 157.0, 140.4, 140.2,
137.7, 131.1, 130.1, 129.2, 128.1, 121.9, 120.8, 64.7, 24.3.
2-(6-Methoxy-2-pyridinyl)phenylmethanol 7d. Anal.
Calcd. for C13H13NO2: C, 72.5; H, 6.1; N, 6.5. Found: C,
72.8; H, 5.9; N, 6.9 %. MS–ESI? [m/z]: 216.1 (M ? H)?.
1H NMR (400 MHz, CDCl3): d 7.73 (t, J = 6.4 Hz, 1H),
7.50–7.52 (m, 2H), 7.42–7.48 (m, 2H), 7.15 (d,
J = 6.4 Hz, 1H), 6.81 (d, J = 8.4 Hz, 1H), 5.44 (br, 1H),
4.55 (s, 2H), 4.00 (s, 3H). 13C NMR (100 MHz, CDCl3):
163.3, 157.4, 139.9, 139.8, 139.7, 130.6, 130.4, 129.2,
128.2, 117.1, 109.7, 64.5, 53.8.
˚
radiation (k = 0.71073 A) at ambient temperature. The
data were corrected for Lorentz-polarization factors as well
as for absorption. Structures were solved by direct methods
and refined by full-matrix least-squares methods on F2 with
the SHELXL-97 program [27]. The hydroxymethyl group
in 2 was disordered over two positions with occupancies of
0.567(7):0.433(7); it is also refined isotropically. Crystal
data, as well as details of data collection and refinements,
are summarized in Table 1. The CCDC deposition numbers
are 14,44,953 and 14,44,954 for 2 and 3, respectively.
These data can be obtained free of charge from the Cam-
2-(5-Trifluoromethyl-2-pyridinyl)phenylmethanol 7e.
Anal. Calcd. for C13H10F3NO: C, 61.7; H, 4.0; N, 5.5.
Found: C, 61.9; H, 3.7; N, 5.3 %. MS–ESI? [m/z]: 254.1
(M ? H)?. 1H NMR (400 MHz, CDCl3): d 8.85 (d,
J = 4.0 Hz, 1H), 7.87 (s, 1H), 7.48–7.58 (m, 5H), 5.66 (br,
1H), 4.50 (s, 2H). 13C NMR (100 MHz, CDCl3): 160.6,
149.3, 140.3, 139.5, 139.7, 138.5, 131.5, 130.1, 128.5,
126.9, 123.8, 121.6, 119.6, 117.8, 64.4.
Results and discussion
Synthesis and structures of complexes 2 and 3
The water-soluble palladacycles 2 and 3 were easily pre-
pared via the bridge-splitting reactions of dimer 1 with
PPh3 or Sphos (Scheme 1). They were characterized by
elemental analysis, MS, 1H and 13C NMR. The NMR
spectra of these complexes are consistent with the proposed
structures. In the mass spectra of 2–3, the most intense
peak was attributed to [M–Cl]. In addition, the structures of
both complexes have been determined by X-ray single-
crystal diffraction.
2-(5-Acetyl-2-pyridinyl)phenylmethanol 7f. Calcd. for
C14H13NO2: C, 74.0; H, 5.8; N, 6.2. Found: C, 74.4; H, 5.6;
N, 6.5 %. MS–ESI? [m/z]: 228.1 (M ? H)?. 1H NMR
(400 MHz, CDCl3): d 9.21 (d, J = 1.2 Hz, 1H), 8.40 (d,
J = 6.4 Hz, 1H), 7.76 (d, J = 6.4 Hz, 1H), 7.59 (d,
J = 6.0 Hz, 1H), 7.53 (d, J = 6.0 Hz, 1H), 7.43–7.51 (m,
2H), 5.90 (br, 1H), 4.50 (s, 2H), 2.71 (s, 3H). 13C NMR
(100 MHz, CDCl3): 196.0, 162.9, 148.6, 140.5, 138.8,
137.0, 131.5, 130.6, 130.3, 130.2, 128.4, 123.8, 64.5, 26.8.
Both palladacycles adopt a trans-geometry in the solid
state. The molecules are shown in Figs. 1 and 2. The Pd
123