New Phenylbis(salicylato)bismuth(III) Complexes
Organometallics, Vol. 26, No. 14, 2007 3327
N2. In a separate Schlenk flask salicylic acid (275 mg, 2.0 mmol)
was loaded. After the flasks were removed from the drybox and
purged with Ar, 200 mL of dry acetone was added into each flask.
The three-neck flask containing BiPh3 was heated to reflux, and
then the solution of the acid was added dropwise over a period of
3 h. The mixture was stirred at reflux for an additional 1 h, and
then the resulting solution was cooled to ambient temperature. The
solvent was removed, and the product was washed with dry toluene
and diethyl ether and then dried in vacuo. A white solid of 1a
was obtained. Yield: 510 mg, 91%. Anal. Calcd (found) for
BiC20H15O6: C, 42.87 (42.43); H, 2.70 (2.60). 1H NMR
(d6-dmso): δ 6.83-6.87 (m, 4H, salH), 7.38 (m, 1H, Ph + 2H,
Hsal), 7.78 (d, 2H, Hsal, J ) 7.4 Hz), 7.94 (t, 2H, Ph, J ) 7.4 Hz),
8.83 (d, 2H, Ph, J ) 7.4 Hz), 12.17 (s, 2H, salH, OH). 13C{1H}
NMR (d6-dmso): δ 174.41, 160.70, 137.25, 134.28, 132.38, 130.69,
128.05, 118.58, 117.03, 116.74.
(found) for BiC32H29N2O6: C, 51.48 (51.94); H, 3.92 (3.98); N,
1
3.75 (3.61). Mp: 149-151 dec. H NMR (d6-dmso): δ 2.26 (s,
6H, HsalMe), 6.65-6.67 (m, 4H, Hsal4Me), 7.36 (t, 1H, Ph), 7.48
(dd, 2H, bipy), 7.62 (m, 2H, HsalMe) 7.95 (m, 2H Ph + 2H bipy),
8.39 (d, 2H, bipy), 8.69 (d, 2H, bipy), 8.78 (d, 2H, Ph), 12.23 (s,
2H, Hsal4Me).
Complex 3. The compound [3]2‚2Me2CO was obtained in 85%
yield by reacting 331 mg (0.5 mmol) of “Bi(Hsal4Me)3”, prepared
by the solid-state reaction described in the literature,8 and 90 mg
(0.5 mmol) of phen in 20 mL of dry acetone. The crude compound
obtained by this procedure contains small amounts of 2b‚Me2CO.
Anal. Calcd (found) for BiC31H29N2O7: C, 49.61 (50.32); H, 3.89
(3.76); N, 3.73 (3.49).
Complex 4. The compound [4]2‚4Me2CO was prepared as for
[3]2‚2Me2CO, using bipy instead of phen. Traces of 2d were
detected in the crude product of the reaction. Anal. Calcd (found)
for BiC42H44N2O11: C, 51.23 (52.18); H, 4.73 (3.80); N, 2.99 (3.04).
Complex 5. Compound 5 was obtained using a procedure similar
to that described for [Bi(Hsal)(sal)(phen)‚C7H8]2 by reacting Bi-
Complex 1b. Complex 1b was prepared as described for 1a from
BiPh3 (440 mg, 1 mmol) and H2sal4Me (304 mg, 2 mmol) and was
obtained as a pale yellow solid. Yield: 526 mg, 89%. Anal. Calcd
(found) for BiC22H19O6: C, 44.91 (44.84); H, 3.25 (2.85). 1H NMR
(d6-dmso): δ 2.25 (s, 6H, HsalMe), 6.63 (d, 2H, Hsal4Me, J ) 7.3
Hz), 6.67 (s, 2H, Hsal4Me), 7.37 (t, 1H, Ph, J ) 7.4 Hz), 7.64 (d,
2H, Hsal4Me, J ) 7.8 Hz), 7.92 (t, 2H, Ph, J ) 7.6 Hz), 8.81 (d,
2H, Ph, J ) 7.0 Hz), 12.19 (s, 2H, salH, OH). 13C{1H} NMR
(d6-dmso): δ 173.99, 160.17, 144.24, 136.74, 131.81, 130.05,
127.50, 119.17, 116.39, 113.92, 20.79.
(Hsal4Me
)
and phen in dry MeOH.3 Anal. Calcd (found) for
3
BiC37H35N2O10: C, 50.69 (50.44); H, 4.02 (3.71); N, 3.20
(3.24).
Reaction of BiPh3 with H2sal in Reagent-Grade Acetone.
When the acidolysis reaction of BiPh3 with H2sal as described for
1a was performed using reagent grade “wet” acetone, the resulting
solution was slightly turbid. Filtration and concentration of the
filtrate to approximately 1/10 of the initial volume resulted in a
clear solution, which upon standing deposited large colorless crystals
of [Bi38O44(Hsal)26(Me2CO)16(H2O)2]‚4Me2CO in almost quantita-
tive yield: Pbca, a ) 31.692(3) Å, b ) 31.215(3) Å, c ) 31.881-
(3) Å, V ) 31539 (9) Å3.
Complex 2a. To a solution of 1a (280 mg, 0.5 mmol) in 10 mL
of dry acetone was added via syringe a solution of phen (90 mg,
0.5 mmol) in 8 mL of the same solvent at 25 °C. The mixture was
stirred for an additional 30 min, concentrated to approximately half
of the initial volume, and left overnight at -20 °C, during which
time a white solid deposited in the flask. The product was washed
with dry diethyl ether and dried in vacuo to give 326 mg (88%) of
the title compound. Anal. Calcd (found) for BiC32H23N2O6: C,
51.90 (51.52); H, 3.13 (3.32); N, 3.78 (3.99). Mp: 215-217 °C.
1H NMR (d6-dmso): δ 6.84-6.86 (m, 4H, salH), 7.27 (t, 1H, Ph),
7.37 (m, 2H, Hsal), 7.78 (m, 2H, Hsal), 7.86 (d, 2H, phen), 8.00
(t, 2H, Ph), 8.13 (s, 2H, phen), 8.75 (m, 2H Ph + 2H phen), 9.37
(d, 2H, phen), 12.58 (s, 2H, Hsal). 13C NMR (d6-dmso): δ 116.55,
117.20, 118.21, 120.45, 124.22, 127.91, 128.32, 130.51, 131.12,
132.24, 133.89, 136.73, 137.34, 149.28, 155.20, 160.68,
173.73.
Reaction of BiPh3 with H2sal4Me in Reagent-Grade Acetone.
The reaction of BiPh3 with 2 equiv of H2sal4Me in reagent-grade
“wet” acetone produced a very soluble viscous oil. Extended drying
in vacuo resulted in the formation of crystals, which unfortunately
were not suitable for crystallography.
X-ray Structural Determinations. Single crystals of 2a, 2b‚
Me2CO, 2c, 2d‚DMF, [3]2‚2Me2CO, [4]2‚4Me2CO and 5 suitable
for X-ray crystallography were separated as small plates or needles
either directly from the aforementioned reactions or recrystallized
from the corresponding solvents. X-ray crystallographic data are
given in Table 1. The data for 2a, 2b‚Me2CO, 2d‚DMF, [3]2‚2Me2-
CO, [4]2‚4Me2CO, and 5 were collected at 298, 223, or 195 K on
a Bruker SMART 1000 CCD diffractometer in a hemisphere with
10-30 s exposure times, while the data for 2c were run on a Bruker
SMART21 CCD system at 190(2) K. The frames were processed
with the SAINT software and corrected for Lorentz and polarization
effects and absorption using Blessing’s method and crystal faces
as incorporated into the program SADABS.22 The structures were
solved using direct methods and refined by full-matrix least squares
on F2 using SHELXL.23 A series of least-squares difference Fourier
cycles were required to locate the remaining non-hydrogen atoms.
The structure refinement of 2c was affected by disorder, as indicated
by the large anisotropic displacement parameters for several
salicylate and phen molecules due to the structure suffering from
excessive libration. Disorder ratios were all determined to be 50:
50. All non-hydrogen atoms were refined anisotropically, either
independently or via EADP commands when they overlapped
Complex 2b. A solution of phen (135 mg, 0.75 mmol) in acetone
(15 mL) was added to a round-bottom flask containing 1b
(441 mg, 0.75 mmol) in 15 mL of the same solvent at 25 °C. Upon
completion of the addition, the reaction mixture was stirred for 30
min and then concentrated to approximately half of the initial
volume and kept overnight at -20 °C to give a white solid. The
product was filtered, washed with dry toluene and diethyl ether,
and dried in vacuo. Yield: 483 mg (84%). Anal. Calcd (found) for
BiC34H29N2O6: C, 52.99 (52.82); H, 3.79 (3.38); N, 3.64 (3.49).
1H NMR (d6-dmso): δ 2.24 (s, 6H, Hsal4Me), 6.68 (m, 4H, Hsal4Me),
7.22 (t, 1H, Ph), 7.72 (m, 2H Hsal4Me + 2H phen), 7.76 (t, 2H,
salH) 8.00 (2H, d, phen), 8.72-8.76 (m, 2H Ph + 2H phen), 9.37
(d, 2H, phen) 12.32 (s, 2H, salH4Me). Mp: 204-206 °C dec.
Complex 2c. The compound was synthesized from 1a (280 mg,
0.5 mmol) and bipy (78 mg, 0.5 mmol) using the same conditions
and procedures as for 2a. A white solid was obtained (309 mg,
86%). Anal. Calcd (found) for BiC30H23N2O6: C, 50.29 (50.34);
1
(21) SMART (Version 5.04) and SAINT (Version 7.23a); Bruker AXS
Inc., Madison, WI, 2002.
(22) (a) Blessing, R. H. Acta Crystallogr. 1995, A51, 33. (b) Sheldrick,
G. M. SADABS (Version 5.1); Universita¨t Go¨ttingen, Go¨ttingen, Germany,
1997. (c) Sheldrick, G. M. SADABS, Siemens Area Detector Absorption
Correction, Version 2006/1; Universita¨t Go¨ttingen, Go¨ttingen, Germany,
2006.
(23) (a) Sheldrick, G. M. SHELXTL, Version 6.1; Universita¨t Go¨ttingen,
Go¨ttingen, Germany, 2002. (b) Sheldrick, G. M. SHELXS97 and SHELXL97;
Universita¨t Go¨ttingen, Go¨ttingen, Germany, 1997.
H, 3.24 (3.32); N, 3.91 (3.99). H NMR (d6-dmso): δ 6.77-6.81
(m, 4H, salH), 7.18 (t, 1H, Ph), 7.38 (m, 2H, Hsal), 7.46 (m, 2H,
bipy), 7.74 (m, 2H, Hsal), 7.93 (m, 2H Ph + 2H bipy), 8.40 (d,
2H, bipy), 8.71 (d, 2H Ph), 8.81 (d, 2H, bipy), 12.32 (s, 2H, Hsal).
Mp: 196-198 °C.
Complex 2d. Complex 2d was prepared as described for 2b by
the addition of bipy (117 mg, 0.75 mmol) to 1b (441 mg,
0.75 mmol) in dry acetone. Yield: 453 mg (81%). Anal. Calcd