1
50
M. Rajabi et al. / Inorganica Chimica Acta 432 (2015) 149–157
have been also compared. The molecular descriptors derived from
the electron density properties and computed at the bond critical
points as defined by quantum theory of atoms in molecules
2.4. Crystal structure determination
Suitable single crystals of C were mounted on a glass fibre.
1
(
QTAIM) analysis, have been used to gain some insights into the
Data collections were carried out at room temperature on a
Bruker-Nonius Kappa-CCD-diffractometer equipped with gra-
Mn–L interactions. Additionally, the effectiveness of C as a
1
catalyst for the epoxidation of some alkenes is demonstrated. To
our knowledge, this is the first report on the catalytic activity of
Mn–CAPh complex in epoxidation reactions.
phite-monochromatized Mo Ka radiation (k = 0.71073 Å). Cell
parameters were retrieved and refined using the DENZO-SMN [29]
software on all reflections. Data reduction was performed with
the DENZO-SMN software. The structure was solved by SIR2004 [30]
and refined with the program SHELXL-2014/7 [31]. After obtaining
the anisotropic refinement of the structural model, the remaining
residua suggested very disordered methanol molecules. So, by
computing the mass and number of electrons in the obvious void
by means of the SQUEEZE-option of the PLATON-program [32], it was
found that the complex is solvated with six methanol molecules
per formula unit (a reasonable simplification in view of the possi-
ble loss of solvent). According to the SQUEEZE-results, thirty-four
molecules of methanol were included in the final refinement as a
fixed contribution.
All non-hydrogen atoms were refined anisotropically. Three of
the pyrrolidine rings were split into two orientations. The major
and minor parts were refined anisotropically, but distance and
similarity restraints (SADI, SIMU and SAME) had to be applied for
a convergent least-square refinement yielding site occupancy
ratios of 0.39(3)/0.61(6), 0.20(3)/0.80(6) and 0.46(7)/0.54(2).
Hydrogen atoms were placed in geometrically idealized positions,
and constrained to ride on their parent atoms. Crystal data and
2
. Experimental
2.1. Materials and methods
All chemicals and solvents were of reagent grade and obtained
commercially without further purification. Melting points were
obtained with an electrothermal instrument. IR spectra were
recorded on a Nicolet 510P spectrophotometer using KBr disk.
NMR spectra were recorded on a Bruker Avance DRX-500 spec-
1
13
trometer. H and C chemical shifts were measured relative to
3
1
the internal TMS, and P chemical shift was determined relative
to 85% H PO as the external standard. The products of oxidation
3
4
reactions were determined and analyzed by an HP Agilent 6890
gas chromatograph equipped with a HP-5 capillary column (phenyl
methyl siloxane 30 m 320 lm 0.25 lm), and a flame ionization
detector.
1
experimental details of the structure determination for C are
listed in Table 1.
0
00
2
.2. Synthesis of N-isonicotinyl, N , N -bis(pyrrolidinyl) phosphoric
triamide, 4-NC C(O)NHP(O)(NC (L)
H
5 4
4 8 2
H )
2.5. Computational details
N-isonicotinyl phosphoramidic
dichloride,
4-
NC
5
H
4
C(O)NHP(O)Cl , was prepared and purified according to the
2
The calculations were carried out using the GAUSSIAN 03 package
33]. Density functional calculation using the Becke’s three param-
eter hybrid functional combined with the Lee–Yang–Parr correla-
tion function (B3LYP) [34] was chosen among the DFT methods
due to its good performance in molecular structure and force field
literature [17]. A solution of pyrrolidine 8 mmol (0.66 mL) in dry
acetonitrile (20 mL) was added dropwise to a solution of 4-
NC H C(O)NHP(O)Cl 2 mmol (0.48 g) in dry acetonitrile (20 mL)
5 4 2
at 0 °C. After 4 h stirring, the solvent was evaporated and the
brown transparent oily residue was washed with acetone to
remove the pyrrolidine salt and the filtrate was powdered by n-
heptane.
[
1
determinations [35]. For C , a fragment related to the all-cis
Yield: 70%. m.p. 164 °C. 1H NMR (500.13 MHz, DMSO-d
):
6
Table 1
d = 1.72–1.82 (m, 8Haliphatic), 3.09–3.20 (m, 8Haliphatic), 7.78 (dd,
Crystallographic data for C1.
5
3
1
3
HH = 4.5 Hz, 2Hpyridine), 8.72 (dd, 6JPH = 1.5 Hz,
J
J
PH = 1.6 Hz,
J
Compound
C
1
2
HH = 4.5 Hz, 2Hpyridine), 9.49 (d, JPNH = 6.5 Hz, 1H, NHamide) ppm.
3
3
Empirical formula
Formula weight
T (K)
C
28
H
42Cl
2
8
N O
4
P
2
4
Mnꢀ6(CH O)
C NMR (125.76 MHz, DMSO-d
6
): d = 25.8 (d,
J
PC = 8.5 Hz), 45.9
PC = 8.7 Hz, Cipso), 150.1 (s),
66.9 (s, C@O) ppm. P NMR (202.46 MHz, DMSO-d ): d = 6.47
934.78
293(2)
2
3
(
d, JPC = 4.9 Hz), 121.8 (s), 141.0 (d, J
1
3
1
6
Crystal system, space group
trigonal, P 3
16.7451(5)
16.7451(5)
25.7864(9)
90
1
2 1
ꢁ
1
(
m) ppm. IR (KBr, cm ): 3075 (mw), 2930 (ms),1678 (s, C@O),
553 (w), 1494 (mw), 1443 (vs), 1268 (ms), 1215 (s), 1179 (s,
P@O), 1111 (m), 1083 (s), 1014 (m), 873 (m), 821 (ms), 748 (m),
a (Å)
b (Å)
c (Å)
1
a
(°)
b (°)
(°)
6
99 (mw), 580 (mw), 538 (mw), 467 (mw).
90
120
c
3
V (Å )
6261.8(4)
6
1.470
0.584
2933
0.2 ꢂ 0.16 ꢂ 0.04
1.61–27.71
9668
5340 [Rint = 0.0450]
0.99/0.55
5340/498/548
0.002(14)
1.026
0
00
Z
D
2
.3. Synthesis of bis-[N-isonicotinyl, N , N -bis(pyrrolidinyl)
calc (Mg m 3
ꢁ
)
phosphoric triamide] Mn(II) dichloride, {Mn[4-NC
5
H
4
C(O)NHP(O)
ꢁ1
Absorption coefficient (mm
F(000)
Crystal size (mm)
)
(
NC
4
H
) ]
8 2 2
2
Cl }
n 3 1
ꢀ34CH OH (C )
h range for data collection (°)
Reflections collected
Independent reflections
Completeness to h (%)
Data/restraints/parameters
Flack parameter
2
MnCl ꢀ4H
2
O 0.5 mmol (0.10 g) was added to a solution of L
mmol (0.31 g) in methanol (15 mL) and stirred for 4 h. Upon slow
evaporation of the filtrate at room temperature, suitable colorless
prism crystals of the complex C were isolated. C is soluble in
1
1
1
ethanol, methanol and acetonitrile.
Goodness-of-fit (GOF) on F2
Final R indices
R indices (all data)
Yield: 50%. m.p. 191–192 °C. IR (KBr, cmꢁ1): 3446 (br), 3096
br), 2965 (m), 2874 (m), 1686 (s, C@O), 1617 (w), 1558 (w),
451 (vs), 1268 (m), 1217 (m), 1166 (m, P@O), 1015 (mw), 917
R
R
1
= 0.0726, wR
= 0.1293, wR
2
= 0.2018
= 0.2523
(
1
(
1
2
ꢁ3
Largest difference in peak and hole (e Å
)
0.522 and ꢁ1.025
w), 820 (mw), 795 (w), 685 (w), 582 (w), 544 (mw), 477 (w).