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Makarov et al.
and an equal volume of benzene was added. Then the solution
was washed several times with water to neutral pH. The organic
phase was dried over MgSO4 and filtered. The solvent was reꢀ
moved on a rotary evaporator. The residue was treated with
petroleum ether. The orange solution in light petroleum was
discarded and the residue was extracted with boiling petroleum
ether (70/100) (3×15 mL) to remove phenylferrocene. Borꢀ
oxine 2 was obtained as a brickꢀred powder in a yield of 0.73 g
ganic layer was washed several times with water, dried with
MgSO4, and filtered. The chloroform was removed in vacuo and
the residue was recrystallized from toluene. Terphenyl 3 was
obtained as darkꢀred needleꢀlike crystals in a yield of 0.15 g
(65%), t.decomp. >250 °C. Found (%): C, 73.04; H, 4.55;
N, 3.01. C28H21FeNO2. Calculated (%): C, 73.22; H, 4.61;
N, 3.05. 1H NMR, δ: 4.06 (s, 5 H); 4.34 and 4.68 (both m,
2 H each); 7.56 and 7.69—7.75 (both m, 4 H each); 7.77—7.79,
8.29—8.32 (both m, 2 H each).
Xꢀray diffraction study. Thin needleꢀlike crystals of the solꢀ
vate 2•2C6H6 were grown by cooling a hot solution of comꢀ
pound 2 in a benzene—hexane mixture to 20 °C. The crystals of
4″ꢀferrocenylꢀ4ꢀnitroꢀ1,1´:4´,1″ꢀterphenyl (3) were grown from
a CHCl3—MeOH mixture. Xꢀray diffraction data were collected
on a SMART Bruker diffractometer (graphite monochromator,
λ(MoꢀKα) = 0.71073 Å). The crystallographic data are given in
Table 4.
The structures of 2•2C6H6 and 3 were solved by direct methꢀ
ods and refined isotropically by the fullꢀmatrix leastꢀsquares
method. The Xꢀray data sets were processes with the use of the
SAINT program.9 The absorption correction was applied using
the SADABS program.10 The final refinement was carried out
by the fullꢀmatrix leastꢀsquares method with anisotropic disꢀ
placement parameters. The positions of the hydrogen atoms
(50%), t.decomp. >270 °C. Found (%): C, 66.87; H, 4.88.
1
C
48H39B3Fe3O3. Calculated (%): C, 66.74; H, 4.55. H NMR,
δ: 4.07 (s, 5 H); 4.39, 4.77, 7.62, and 8.18 (all m, 2 H each).
B. Under the aboveꢀdescribed conditions, boroxine 2 was
prepared in a yield of 0.29 g (50%) starting from 4ꢀbromophenylꢀ
ferrocene (0.68 g, 2 mmol), 1.7 M tertꢀbutyllithium (3 mL,
5.1 mmol), and tributyl borate (0.75 mL, 0.64 g, 2.8 mmol).
4″ꢀFerrocenylꢀ4ꢀnitroꢀ1,1´:4´,1″ꢀterphenyl (3). Dichloroꢀ
bis(triphenylphosphine)palladium(II), Pd(PPh3)2Cl2, (0.0053 g,
0.008 mmol), boroxine 2 (0.144 g, 0.167 mmol), 4´ꢀbromoꢀ4ꢀ
nitroꢀ1,1´ꢀbiphenyl (0.139 g, 0.500 mmol), potassium carbonꢀ
ate (0.14 g), DMF (6 mL), and water (1.5 mL) were successively
placed in a Schlenk flask. The reaction mixture was heated
to 65 °C, vigorously stirred at this temperature for 2 h, and then
cooled to room temperature, after which water was added, and
the product was extracted with chloroform (150 mL). The orꢀ
Table 4. Crystallographic data and details of Xꢀray diffraction study of compounds 2•2C6H6 and 3
Parameter
2•2C6H6
3
Molecular formula
Molecular weight
Crystal system
Space group
C48H39B3Fe3O3•2C6H6
C28H21FeNO2
459.31
Monoclinic
P21
1019.99
Orthorhombic
Pbca
T/K
Z
120(2)
8
298(2)
2
a/Å
b/Å
c/Å
α/deg
10.436(2)
23.419(5)
40.422(8)
90
7.8649(16)
7.6182(15)
17.830(4)
90
β/deg
90
90
9880(3)
1.371
0.916
100.85(3)
90
1049.2(4)
1.454
γ/deg
V/Å3
dcalc/g cm–3
Absorption coefficient, µ/mm–1
0.745
F(000)
4224
476
Scan mode
ω
ω
θ Scan range/deg
Number of measured reflections
Number of independent reflections
Rint
2.02—27.03
52481
10727
0.1912
622
2.64—30.19
9927
5933
0.0737
289
Number of parameters in refinement
GOOF
0.780
0.723
Number of reflections with I ≥ 2σ(I )
3110
1707
Final R factors (for reflections with I ≥ 2σ(I ))
R1
wR2
0.0619
0.1128
0.0506
0.0906
R factors for all reflections
R1
wR2
0.2450
0.1552
—
0.2255
0.1211
0.00(2)
Flack's parameter
Makarov
