Preparations
Anal. calc. for C
Found: C, 51.11; H, 6.69; N, 4.21%.
H
N O W: C, 51.23; H, 6.76; N, 4.27%.
28 44
2 4
2-(2º-Pyridyl)propan-2-ol(HL1).11 To
a solution of 2-
[W O (L 4) ]. Yield: 76%. 1H NMR: d 7.58È7.69 (m, 8 H,
2
2
acetylpyridine (1.94 g, 16.0 mmol) in diethyl ether (30 cm3) at
0 ¡C was added dropwise freshly prepared MeMgI (1.0 M in
diethyl ether, 16.0 cm3, 16.0 mmol). A pale yellow solid formed
during addition and the mixture was stirred at ambient tem-
perature for 2 h. Water (30 cm3) was then added to the
mixture, which was acidiÐed with concentrated HCl until two
clear layers were obtained. The aqueous layer was separated
and extracted with diethyl ether (3 ] 50 cm3). The combined
ArH and PyH), 7.22È7.43 (m, 14 H, ArH and PyH), 7.14 (d,
J \ 7.4, 4 H, ArH), 6.65 (t, J \ 6.5 Hz, 2 H, PyH). IR: l(WO )
2
933s, 902s cm~1. HRMS (LSI): m/z calc. for C
H
N O W
36 29
2 4
[M ] H]` 737.1637, found 737.1621. Anal. calc. for
C
H
N O W: C, 58.71; H, 3.83; N, 3.80%. Found: C,
36 28
2 4
58.79; H, 3.81; N, 3.80%.
[W O (L 5) ]. Yield: 85%. 1H NMR: d 7.54È7.62 (m, 8 H,
2
2
ArH and PyH), 7.29È7.35 (m, 10 H, ArH and PyH), 7.02 (d,
J \ 8.5, 4 H, ArH), 6.55 (t, J \ 6.4 Hz, 2 H, PyH), 1.38 (s, 18
H, tBu), 1.24 (s, 18 H, tBu). 13CM1HN NMR: d 165.3, 151.2,
150.3, 148.4, 144.0, 143.5, 137.9, 128.8, 126.9, 125.0, 124.9,
organic portions were dried over anhydrous MgSO , concen-
trated, and chromatographed using hexanesÈethyl acetate
(3 : 1) as eluent to give the product as a pale yellow liquid.
4
Yield: 1.36 g (62%). 1H NMR: d 8.52 (d, J \ 4.9, 1 H, H ),
124.4, 122.3, 94.5, 34.6, 34.4, 31.4, 31.2. IR: l(WO ) 936s, 904s
a
2
7.71 (t, J \ 7.8, 1 H, H ), 7.39 (d, J \ 7.8, 1 H, H ), 7.20 (dd,
cm~1. HRMS (LSI): m/z calc. for C
H
N O W [M ] H]`
c
b
d
52 61
2
4
J \ 4.9, 7.8 Hz, 1 H, H ), 5.12 (br s, 1 H, OH), 1.55 (s, 6 H,
961.4144, found 961.4271. Anal. calc. for C
H
N O W: C,
52 60
2 4
CH ). 13CM1HN NMR: d 165.9, 147.3, 137.0, 121.8, 118.7, 71.6,
65.00; H, 6.29; N, 2.92%. Found: C, 64.43; H, 6.24; N, 2.52%.
3
30.6.
General procedure for the preparation of [WO (Ln) ]
2
2
General procedure for the preparation of [WO (Ln) ]
(n = 6,7). To a suspension of LiLn (n \ 6, 7) (4È6 mmol) in
2
2
(n = 1–5). To a colourless solution of HLn (n \ 1È5) (2.8È6.0
mmol) in THF (20 cm3) at 0 ¡C was slowly added a solution of
n-BuLi in n-hexane (1.6 M, 1.1 equiv.). For n \ 1, 2 and 4, a
pale brown precipitate formed immediately. The mixture was
stirred at room temperature for 1 h, then a solution of
[WO Cl (DME)] (0.5 equiv.) in THF (20 cm3) was added.
THF (50 cm3) was slowly added
a
solution of
[WO Cl (DME)] (0.5 equiv.) in THF (50È100 cm3) at room
2
2
temperature. For n \ 6, a pale yellow solid appeared during
addition and the suspension was stirred overnight at room
temperature, then Ðltered. The pale yellow solid obtained was
washed thoroughly with THF and dried in vacuo. For n \ 7,
the mixture was stirred at room temperature overnight, then
evaporated under reduced pressure. The reddish brown
residue was extracted with CH Cl (50 cm3) and the extract
2
2
The mixture was stirred overnight at room temperature then
the volatiles were removed under reduced pressure to give a
gray residue that was extracted with CH Cl (50È200 cm3).
2
2
2
2
For n \ 1, 2 and 4, the extract was concentrated to give a
was concentrated and chromatographed using CHCl as
3
solid, which was collected by Ðltration and washed thoroughly
eluent to give a pale yellow solid, which was recrystallised
with CHCl , diethyl ether and hexanes. The resulting white
from CH Cl Èdiethyl ether.
3
2
2
solid was further puriÐed by recrystallisation from DMF (for
[W O (L 6) ]. Yield: 85%. IR: l(WO ) 940m, 898s cm~1.
2
2
2
N O S W: C, 56.26; H, 3.67; N, 3.64;
n \ 1 and 4) or CH Cl (for n \ 2). For n \ 3 and 5, the
Anal. calc. for C
S, 8.34%. Found: C, 56.07; H, 3.99; N, 3.53; S, 7.81%.
H
2
2
36 28
2 2 2
extract was evaporated and chromatographed using ethyl
acetateÈethanol (1 : 1) (for n \ 3) or CH Cl followed with
[W O (L 7) ]. Yield: 43%. 1H NMR (DMSO-d ): d 9.37 (d,
2
2
2
2
6
ethyl acetate (for n \ 5) as eluent. The white solid obtained
J \ 4.8, 2 H, H ), 7.89 (t, J \ 7.7, 2 H, H ), 7.34 (d, J \ 8.7, 4
a
c
was then recrystallised from acetone (for n \ 3) or CHCl (for
H, ArH), 7.30 (d, J \ 8.7, 4 H, ArH), 7.16 (dd, J \ 4.8, 7.7, 2
H, H ), 7.10 (d, J \ 8.7, 4 H, ArH), 6.95 (d, J \ 8.1, 2 H, H ),
6.89 (d, J \ 8.7 Hz, 4 H, ArH), 1.29 (s, 18 H, tBu), 1.24 (s, 18
H, tBu). 13CM1HN NMR: d 170.3, 153.4, 150.1, 149.8, 144.3,
144.0, 137.3, 129.2, 128.8, 127.2, 124.8, 124.4, 122.4, 69.2, 34.4
3
n \ 5).
b
d
[W O (L 2) ]. Yield: 47%. 1H NMR: d 8.77 (d, J \ 5.2, 2 H,
2
2
H ), 7.81 (t, J \ 7.7, 2 H, H ), 7.26È7.31 (m, 4 H, H and H ),
a
c
b
d
2.06È2.28 (m, 6 H, CH ), 1.87 (dq, J \ 14.5, 7.5, 2 H, CH ),
2
2
1.20 (t, J \ 7.5, 6 H, CH ), 0.95 (t, J \ 7.5 Hz, 6 H, CH ).
(two overlapping signals), 31.4, 31.3. IR: l(WO ) 952m, 908s
3
3
2
13CM1HN NMR: d 167.8, 147.4, 138.8, 123.0, 121.0, 90.0, 32.4,
cm~1. Anal. calc. for C
H
N O S W: C, 62.90; H, 6.09; N,
52 60
2 2 2
29.9, 8.7, 8.2. IR: l(WO ) 931s, 893s cm~1. HRMS (LSI): m/z
2.82; S, 6.46%. Found: C, 62.28; H, 5.90; N, 2.76; S, 6.19%.
2
calc. for C
H
N O W [M ] H]` 545.1633, found 545.1693.
20 29
2 4
[W O (L 3) ]. Yield: 83%. 1H NMR: d 9.16 (dd, J \ 1.2, 5.6,
X-Ray crystallographic analysis of [WO (Ln) ] (n = 3–5)
2
a
2
2
2
2 H, H ), 7.81 (dt, J \ 1.2, 7.9, 2 H, H ), 7.67 (d, J \ 7.9, 2 H,
c
H ), 7.42 (dd, J \ 5.6, 7.9 Hz, 2 H, H ), 1.19 (s, 36 H, tBu).
Crystal data and data processing parameters are given in
Table 1. Data were collected at 294È296 K on a MSC/Rigaku
RAXIS IIc imaging plate system using Mo-Ka radiation
(j \ 0.710 73 A) from a Rigaku RU-200 rotating anode gener-
d
b
13CM1HN NMR: d 166.0, 148.5, 136.6, 123.2, 122.7, 100.0, 44.7,
29.8. IR: l(WO ) 908m, 878s cm~1. HRMS (LSI): m/z calc.
2
for C
H
N O W [M ] H]` 657.2888, found 657.2902.
28 45
2
4
Table 1 Crystallographic data for [WO (Ln) ] (n \ 3È5)
2
2
2[WO (L3) ] É 3H O
[WO (L4) ] É 2DMF
[WO (L5) ] É 0.5DMF
2
2
2
2
2
2
2
Formula
Formula weight
Crystal system
Space group
a/A
C
H
N O
W
C
H
N O W
C
997.42
Monoclinic
P2 /n (no. 14)
17.660(3)
16.118(1)
19.974(3)
106.760(3)
5444(1)
4
2.164
7249
7249
0.0845, 0.1741
H
N
O
W
56 94
1367.05
4
11
2
42 42
882.65
4
6
53.5 63.5 2.5 4.5
Monoclinic
P2 /n (no. 14)
20.712(4)
14.805(3)
21.362(4)
111.50(3)
6095(2)
4
3.829
9327
Monoclinic
P2 /c (no. 14)
13.467(3)
24.756(5)
11.723(2)
100.04(3)
3848.5(13)
4
3.054
6301
1
1
1
b/A
c/A
b/¡
U/A
3
Z
k/mm~1
ReÑections collected
Independent reÑections
Final R , wR [I [ 2p(I)]
9327
0.0468, 0.1264
6301
0.0531, 0.1487
1
2
354
New J. Chem., 2001, 25, 353È357