Hypervalent organoselenium(II) compounds with organophosphorus ligands. Crystal and molecular structure of [2-(iPr2NCH2)C 6H4]Se[S2PR′2] (R′ = Ph, OiPr)

Article abstract of DOI:10.1002/zaac.201100165

Redistribution reactions between diorganodiselenides of type [2-(R ₂NCH₂)C₆H₄]₂Se ₂ [R = Et, iPr] and bis(diorganophosphinothioyl disulfanes of type [R′₂P(S)S]₂ (R = P

Full text of DOI:10.1002/zaac.201100165

ARTICLE
DOI: 10.1002/zaac.201100165
Hypervalent Organoselenium(II) Compounds with Organophosphorus
Ligands. Crystal and Molecular Structure of [2-(iPr2NCH2)C6H4]Se[S2PR'2]
(R' = Ph, OiPr)
Elise Duhamel,[a] Alpar Pöllnitz,[b] Adina Stegarescu,[b] and Anca Silvestru*[b]
Keywords: Organoselenium compounds; Organophosphorus ligands; NMR spectroscopy; X-ray diffraction
Abstract. Redistribution reactions between diorganodiselenides of by single-crystal X-ray diffraction. In both compounds the N(1) atom
type [2-(R2NCH2)C6H4]2Se2 [R = Et, iPr] and bis(diorganophosphino- is intramolecularly coordinated to the selenium atom, resulting in T-
thioyl disulfanes of type [R'2P(S)S]2 (R = Ph, OiPr) resulted in the shaped coordination arrangements of type (C,N)SeS. The dithio organ-
hypervalent [2-(R2NCH2)C6H4]SeSP(S)R'2 [R = Et, R' = Ph (1), OiPr ophosphorus ligands act monodentate in both complexes, which can
(2); R = iPr, R' = Ph (3), OiPr (4)] species. All new compounds were be described as essentially monomeric species. Weak intermolecular
characterized by solution multinuclear NMR spectroscopy (1H, 13C, S···H contacts could be considered in the crystal of 3, thus resulting in
31P, 77Se) and the solid compounds 1, 3, and 4 also by FT-IR spectros- polymeric zig-zag chains of R and S isomers, respectively.
copy. The crystal and molecular structures of 3 and 4 were determined
exhibit monomeric structures,[20] while in species of type
Introduction
[2-{Z(CH2CH2)2NCH2}C6H4]Se[S2PR'2] supramolecular ar-
An increased interest towards organoselenium compounds
chitectures realized by weak S···H (Z = MeN, R' = Ph) and
containing an intramolecular E→Se (E = N, O) interaction was
observed during the last years,[1–3] mainly due to their potential
applications in organic synthesis, either as catalysts or as trans-
fer reagents,[4–12] in biology and medicine as enzyme mimics
or chemotherapeutic products,[13–16] in material science as sin-
gle source precursors for CVD processes,[17] etc.
N···H (Z = MeN, R' = OiPr) intermolecular contacts or poly-
meric chains realized by weak O···H interactions (Z = O, R' =
OiPr) were described.[21]
In order to increase the basicity of the coordinating amino
group and to complete our investigations on organoselenium
complexes with dithiophosphorus ligands, we decided to use
The intramolecular E→Se (E = N, O) interaction provides
an increased thermal and hydrolytic stability and favors the
formation of monomeric species. The ability of 2-(N,N-dimeth-
ylaminomethyl)phenyl and related organic ligands to establish
such internal interactions was used to prepare different hyper-
valent organoselenium compounds of type Ar2Se2, ArSeX (X =
the
2-(N,N-diethylaminomethyl)phenyl
group
(2-(Et2NCH2)C6H4) and the 2-(N,N-diisopropylamino-
methyl)phenyl group (2-(iPr2NCH2)C6H4) as organic ligands
with pendant arms that can exhibit a (C,N) coordination to-
wards the selenium atom. Herein we report on the syntheses
and spectroscopic characterization of new hypervalent com-
pounds of type [2-(R2NCH2)C6H4]Se[S2PR'2] [R = Et, R' = Ph
(1), OiPr (2); R = iPr, R' = Ph (3), OiPr (4)].
halogen), ArSeL (L
=
dithio ligand) or metal
arylselenolates.[7–15,17,18]
Recently, we reported on the synthesis, solution behavior and
molecular structures of various hypervalent organoselenium
[19,20]
compounds containing the 2-(Me2NCH2)C6H4
and
2-{Z(CH2CH2)2NCH2}C6H4 (Z = O, NMe)[21,22] groups as well
as metal organoselenolates containing the fragment
[2-(R2NCH2)C6H4]SeM (R = Me, Et; M = Au, Zn, Cd).[17,18]
Results and Discussion
The diorganodithiophosphinato (1 and 3) and the diorganod-
ithiophosphato (2 and 4) derivatives were obtained by redistri-
The
organoselenium
compounds
bution
reactions
between
the
diorganodiselenides
[2-(Me2NCH2)C6H4]Se[S2PR'2] (R' = Ph, OiPr) were found to
[2-(R2NCH2)C6H4]2Se2 (R = iPr or Et), with the corresponding
bis(diorganophosphinothioyl)disulfane [R'2P(S)S]2 (R' = Ph,
OiPr), according to the reaction depicted in Equation (1). Ex-
cept compound 2, which is an orange oil, all the other com-
pounds are stable, yellow crystalline solids. Elemental analysis
and NMR spectroscopic data are in agreement with the antici-
pated formulas. The solution behavior of the new compounds
1–4 was investigated by multinuclear (1H, 13C, 31P, 77Se) NMR
spectroscopy at room temperature.
* Prof. Dr. A. Silvestru
Fax: +40-264-590-818
E-Mail: ancas@chem.ubbcluj.ro
[a] Institut Universitaire de Technologie, Departement de Chimie
Université de Rouen
Rue Lavoisier
76821 Mont Saint Aignan Cedex, France
[b] Facultatea de Chimie si Inginerie Chimica
Universitatea Babes-Bolyai
400028 Cluj-Napoca, Romania
Z. Anorg. Allg. Chem. 2011, 637, 1355–1360
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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ARTICLE
The 77Se chemical shifts of compounds 1–4, as well as for
the other related species containing dithiophosphorus ligands
and listed in Table 1, are in agreement with a deshielding with
respect to the corresponding diselenides. The δ77Se values are
intermediate between the values observed for the diaryl disele-
nides used as starting materials and the corresponding arylsele-
nium halides (i.e. δ77Se for [2-(R2NCH2)C6H4]SeCl, R = Et,
1016.7 ppm; R = Me 1030 ppm[19,28]), in accordance with the
lower electronegativity of the dithiophosphorus ligands in
comparison with the X– groups (X = Cl, Br, and I).
The IR spectra for compounds 1, 3, and 4 exhibit strong
absorption bands in the regions 660–640 and 550–500 cm–1,
which were assigned to asymmetric and symmetric ν(PS2)
stretching vibrations in the dithiophosphorus ligands attached
to the organoselenium(II) moieties.
1
The H and 13C NMR resonances were assigned using 2D
NMR experiments, according to the diagram depicted in
Scheme 1.
Single crystals of 3 and 4 suitable for X-ray diffraction stud-
ies were obtained by slow diffusion of n-hexane into a CH2Cl2
solution. The molecular structures are depicted in Figure 1 and
Figure 2, respectively, and selected interatomic distances and
angles are listed in Table 2.
Compounds 3 and 4 can be described as hypervalent 10-Se-
3 species.[29] Both organoselenium compounds are monomeric
and each of them exhibits a strong intramolecular N→Se coor-
dination [N(1)–Se(1) 2.675(4) Å in 3 and 2.662(7) Å in 4; cf.
the sum of the corresponding van der Waals radii, ΣrvdW(Se,N)
3.54 Å[30]], trans to the selenium–sulfur bond [N(1)–Se(1)–
S(1) 174.45(8)° in 3 and 176.92(8)° in 4, respectively], thus
resulting in a distorted T-shaped [(C,N)SeS core] coordination
arrangement around the selenium atom. The N→Se interac-
tions are slightly larger than those observed for other related
Scheme 1. Numbering scheme for NMR resonance assignments.
1
The room temperature H and 13C NMR spectra show the
expected resonances for the organic groups attached to sele-
nium and to phosphorus atoms, respectively. In all spectra the
resonances are split in two components of equal intensity, due
to phosphorus–proton and phosphorus–carbon couplings, re-
spectively. In all investigated phosphorus-containing species,
as well as in the corresponding diselenides,[17,23] no evidence
for an intramolecular N→Se coordination was observed in the
1H NMR spectra. In the aliphatic region the two organic groups
attached to the nitrogen atoms, as well as the CH2 benzylic
protons, respectively, appear to be equivalent in solution at the
NMR time scale. This should be consistent either to the ab-
sence of any N→Se interaction or to a very fast process involv-
ing dissociation and regeneration of the internal N→Se interac-
tion, with pyramidal inversion at the central nitrogen atom.[24]
The isopropoxy groups attached to phosphorus atoms in com-
pounds 2 and 4 exhibit a pattern, which is indicative for their
diastereotopic nature, i.e. two doublet resonances for the HA
and HB methyl protons, respectively.
compounds: [2-(Me2NCH2)C6H4]SeSP(S)R2 [R
=
Ph
2.359(2) Å, OiPr
R
=
2.397(2) Å[20]],
[2-{Z(CH2CH2)2NCH2}C6H4]SeSP(S)R2 [Z = O, R = OiPr
2.557(7) Å; Z = MeN, R = Ph 2.463(4) Å, R = OiPr
2.529(3) Å[21]]. The distortion of the coordination arrangement
is mainly determined by constrains arising from the five-mem-
bered C3NSe chelate rings, particularly the C(1)–Se(1)–N(1)
angle 77.52(1)° in 3 and 76.89(1)° in 4, respectively]. The
overall coordination arrangement around the selenium atom
can be considered as distorted pseudo-trigonal bipyramidal,
with C(1) and the two lone pairs in equatorial positions.
The five-membered C3SeN chelate rings in both compounds
are not planar, the nitrogen atom being displaced out of the
best plane defined through the residual C3Se system [dihedral
angle C3Se/SeNC 42.9(2)° in 3 and 44.54(2)° in 4, respec-
tively]. The N→Se intramolecular coordination induces planar
chirality (with the aromatic ring and the nitrogen atom as chiral
plane and pilot atom, respectively). As a consequence, the
compounds crystallize as 1:1 mixtures of RN and SN isomers.
The internal N→Se interactions are stronger in 3 and 4 than
in the diselenide used as starting material, i.e. 2.675(4) Å in 3
The 77Se NMR chemical shifts for compounds 1–4 are in the
range 587–628 ppm (Table 1), low field shifted in comparison
with the starting diorganodiselenides, [2-(Et2NCH2)C6H4]2Se2
and [2-(iPr2NCH2)C6H4]2Se2, thus indicating the formation of
the selenium–sulfur bonds. A similar behavior was observed in
case of the derivatives 2-[Z(CH2CH2)2NCH2]C6H4SeSP(S)R'2[21]
and 2-[Me2NCH2]C6H4SeSP(S)R'2 (Table 1). The 31P NMR reso-
nances are high field, in case of the dithiophosphato, and low field,
in case of the dithiophospinato derivatives, respectively, shifted in
comparison with the starting disulfanes, [([Ph2P(S)S]2 and
[(iPrO)2P(S)S]2, respectively, as it was also observed for the related
species [2-(Me2NCH2)C6H4]SeSP(S)R'2 (R' = Ph, OiPr[20]) and
2-[Z(CH2CH2)2NCH2]C6H4SeSP(S)R'2 (Z = NMe or O, R' = Ph,
OiPr[21]) (see Table 1).
and 2.662(7) Å in
4 versus 2.782 and 2.988 Å in
[2-(iPr2NCH2)C6H4]2Se2.[23] This behavior is in agreement
with the slightly higher electronegativity of the S(1) atom
placed in trans to the N(1) atom in the N–Se–S fragment and
with the better leaving group character of the dithiophosphorus
ligand compared to an ArSe– group.
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Hypervalent Organoselenium(II) Compounds with Organophosphorus Ligands
Table 1. 31P and 77Se NMR spectroscopic data for compounds of type RSeSP(S)R'2 and the corresponding starting materials.
Compound
77Se NMR
31P NMR
Ref.
[2-(Me2NCH2)C6H4]2Se2
430.0
427.4
406.0
424.0
425.4
[25]
[17]
[23]
[22]
[22]
[26]
[27]
[20]
[20]
[2-(Et2NCH2)C6H4]2Se2
[2-(iPr2NCH2)C6H4]2Se2
[2-{O(CH2CH2)2NCH2}]2Se2
[2-{MeN(CH2CH2)2NCH2}]2Se2
[Ph2P(S)S]2
69.6
81.6
65.1
90.0
64.0
64.0
88.8
86.2
65.3
65.3
87.7
88.2
[(iPrO)2P(S)S]2
[2-(Me2NCH2)C6H4]SeS(S)PPh2
[2-(Me2NCH2)C6H4]SeS(S)P(OiPr)2
[2-(Et2NCH2)C6H4]SeS(S)PPh2
[2-(iPr2NCH2)C6H4]SeS(S)PPh2
[2-(Et2NCH2)C6H4]SeS(S)P(OiPr)2
[2-(iPr2NCH2)C6H4]SeS(S)P(OiPr)2
[2-{O(CH2CH2)2NCH2}C6H4]SeSP(S)Ph2
[2-{MeN(CH2CH2)2NCH2}C6H4]SeSP(S)Ph2
[2-{O(CH2CH2)2NCH2}C6H4]SeS(S)P(OiPr)2
[2-{MeN(CH2CH2)2NCH2}C6H4]SeS(S)P(OiPr)2
617.7a
635.0a
608
a)
–
a)
569
–
a)
628
–
a)
587
–
552.1
562.8
573.9
585.1
[21]
[21]
[21]
[21]
a) This work.
Table 2. Selected bond lengths /Å and angles /° for compounds 3 and
4, as determined by single-crystal X-ray diffraction.
3
4
Se(1)–C(1)
1.944(4)
2.675(4)
2.265(2)
2.089(2)
1.945(2)
77.52(1)
98.30(14)
174.45(8)
99.64(6)
116.81(8)
113.7(4)
114.8(4)
111.8(4)
105.72(24)
91.13(24)
117.14(25)
1.928(4)
2.662(7)
2.249(1)
2.056(2)
1.913(2)
76.89(1)
100.23(12)
176.92(8)
100.46(6)
110.84(8)
112.9(3)
114.9(3)
113.3(3)
106.24(25)
90.71(21)
116.2(2)
Se(1)–N(1)
Se(1)–S(1)
P(1)–S(1)
P(1)=S(2)
C(1)–Se(1)–N(1)
C(1)–Se(1)–S(1)
N(1)–Se(1)–S(1)
P(1)–S(1)–Se(1)
S(1)–P(1)–S(2)
C(11)–N(1)–C(7)
C(11)–N(1)–C(8)
C(7)–N(1)–C(8)
C(11)–N(1)–Se(1)
C(7)–N(1)–Se(1)
C(8)–N(1)–Se(1)
Figure 1. ORTEP representation at 30 % probability and atom num-
bering scheme for the R-3 isomer; hydrogen atoms are omitted for
clarity.
The dithiophosphorus ligands act as monodentate, monome-
tallic monoconnective moieties in both complexes. They are
connected to selenium through S(1) [Se(1)–S(1) 2.265(2) Å in
3 and 2.249(1) Å in 4], whereas the second sulfur atom is
pushed far away from the coordination sphere of the selenium
atom [Se(1)–S(2) 4.007(3) Å in 3 and 5.081(2) Å in 4, versus
ΣrvdW(S,Se) 3.85 Å[30]]. The internal N→Se interaction pre-
vents any intra- or intermolecular secondary interaction be-
tween selenium and the sulfur atoms of the organophosphorus
ligand, by contrast with the situation found in the polymeric
PhSeSP(S)Ph2, where the dithiophosphinato ligand acts ani-
sobidentate, as a bimetallic triconnective moiety, with the same
sulfur atom bridging two selenium atoms from neighboring
molecules.[21]
The Se(1)–S(1) bond lengths are within the expected range
for covalent selenium–sulfur single bonds, similarly with the
values found in other related compounds, i.e.
[2-(Me2NCH2)C6H4]SeSP(S)R2 [R = Ph 2.340(7) Å, R = OiPr
Figure 2. ORTEP representation at 30 % probability and atom num-
bering scheme for the R-4 isomer; hydrogen atoms are omitted for
clarity.
Z. Anorg. Allg. Chem. 2011, 1355–1360
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E. Duhamel, A. Pöllnitz, A. Stegarescu, A. Silvestru
ARTICLE
(R = Et[17], iPr[23]) and the bis(diorganophosphinothioyl)disulfanes,
[R'2P(S)S]2 (R' = Ph[26], OiPr[27]) were prepared according to published
methods. All other reagents were obtained from Aldrich or Merck and
were used as received.
2.337(1) Å[20]] [2-{Z(CH2CH2)2NCH2}C6H4]SeSP(S)R2 [Z =
O, R = OiPr 2.256(7) Å; Z = MeN, R = Ph 2.297(1) Å, R =
OiPr 2.277(1) Å[21]], but longer than in PhSeSP(S)Ph2
[2.205(2) Å[21]] due to the trans effect of the internal N→Se
interaction.
Multinuclear NMR spectra were recorded at room temperature, in dry
CDCl3, with a BRUKER DRX 400 instrument operating at 400.1,
100.61, 161.97, and 76.31 MHz for 1H, 13C, 31P and 77Se, respectively.
The phosphorus–sulfur distances within the ligand moieties
are consistent with single P–S and double P=S bonds: P(1)–
S(1) 2.089(2) Å in 3 and 2.056(2) Å in 4, P(1)=S(2) The 1H and 13C chemical shifts are reported in ppm relative to the
residual peak of the solvent (ref. CHCl3: 1H 7.26, 13C 77.0 ppm),
1.945(2) Å in 3 and 1.913(2) Å in 4, cf. P–S 2.077(1) and
whereas 31P chemical shifts are reported relative to H3PO4 85 %. The
77Se spectra were obtained using diphenyl diselenide as external stand-
ard. Chemical shifts are reported relative to dimethyl selenide (δ = 0)
by assuming that the resonance of the standard is at δ = 461.[32] 1H
and 13C resonances were assigned using 2D NMR experiments (COSY,
HMQC and HMBC). The NMR spectra were processed with the Mes-
tReC and MestReNova software.[33] Infrared spectra in the range 400–
4000 cm–1 for compounds 1, 3 and 4 were recorded with a Jasco FTIR
machine, using KBr pellets. Elemental analyses were performed with
P=S 1.954(1) Å in Ph2P(S)SH,[31] similarly to the situations
observed in the other related compounds.[20,21]
In the crystal of compound 3 the second sulfur atom is also
involved in weak S(2)···Hphenyl contacts (S(2)···H(17')
2.952(4) Å, cf. ΣrvdW(S,H) 3.05 Å,[30] thus resulting in poly-
meric chains of R and S isomers, respectively (Figure 3). No
further interactions between these chains were observed in the
crystal of compound 3. Weak S···H interactions were previ-
ously
found
in
the
related a VarioEL analyzer. Melting points were measured with an Electrother-
mal 9200 apparatus and are not corrected.
[2-{MeN(CH2CH2)2NCH2}C6H4]SeSP(S)R2 (R = Ph, OiPr),
For these species polymeric associations containing both R and
S isomers in the same chain are built.[21]
Crystal Structure Determination: The details of the crystal structure
determination and refinement for compounds 3 and 4 are given in
Table 3. Data were collected with a Bruker SMART APEX diffractom-
eter by using graphite-monochromated Mo-Kα radiation (λ
=
0.71073 Å). Single-crystals of 3 and 4 were attached with Paratone N
oil on cryoloops and the data were collected at room temperature
(297 K). The structures were refined with anisotropic thermal parame-
ters. The hydrogen atoms were refined with a riding model and a mu-
tual isotropic thermal parameter. For structure solving and refinement
the software package SHELX-97 was used.[34] The drawings were cre-
ated with the Diamond program.[35]
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge Crystal-
lographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ,
UK. Copies of the data can be obtained on quoting the depository
numbers CCDC-816418 and CCDC-816419 (Fax: +44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Figure 3. View of the chain polymer based on S···H contacts between
R isomers in the crystal of 3 (only hydrogens involved in intermolecu-
lar contacts are shown) [symmetry equivalent atoms (2.5 – x, –0.5 +
y, 0.5 – z) are given by “prime”].
Synthesis of [2-(Et2NCH2)C6H4]SeSP(S)Ph2 (1): Stoichiometric
amounts of [2-(Et2NCH2)C6H4]2Se2 (0.406g, 0.8 mmol) and
[Ph2P(S)S]2 (0.433g, 0.8 mmol) were stirred in dichloromethane
(40 mL) for 12 h, at room temperature. The resulting yellow solution
was concentrated under vacuum pump to minimum volume. Hexane
was added and the title compound deposited at –25 °C as a microcrys-
talline yellow solid. Yield: 0.713g (85 %). M.p. 81–82 °C.
C23H26NPS2Se (M = 490.52): calcd. C 56.32, H 5.34, N 2.86 %; found:
Conclusions
1
Replacement of methyl by ethyl or isopropyl groups at the
nitrogen atom of the pendant arm in hypervalent organosele-
nium(II) complexes of the type [2-(R2NCH2)C6H4]SeS(P)SR'2
(R = Me, Et, iPr, R' = Ph, OiPr) does not affect dramatically
the structure. A strong internal N→Se interaction is established
in solid state, thus resulting in a distorted T-shaped (C,N)SeS
core. The strength of the N→Se interaction in solid state seems
not to be sensitive to the change of methyl by isopropyl groups
in the pendant arm.
C 56.41, H 5.28, N 2.88 %. H NMR: δ = 0.97 (t, 6 H, NCH2CH3,
3
3JHH = 6.7 Hz), 2.59 (q, 4 H, N-CH2CH3, JHH = 6,6 Hz), 3.51 (s, 2
H, CH2N), 6.95 (d, 1 H, C6H4, H3, 3JHH = 5.8 Hz), 7.04 (m, 2 H, C6H4,
H
4,5), 7.33 (m, 6 H, C6H5-meta + para), 7.79 (d, 2 H, C6H4, H6, 3JHH
=
3
3
6.8 Hz), 7.93 (dd, 4 H, C6H5-ortho, JPH = 12.5, JHH = 7.0 Hz). 13C
NMR: δ = 9.95 (s, NCH2CH3), 44.58 (s, NCH2CH3), 58.64 (s, CH2N),
125.77 (s, C4), 126.58 (s, C3), 127.93 (d, C6H5-meta, JPC = 12.8 Hz),
3
130.49 (s, C6), 131.09 (s, C6H5-para+C5), 131.62 (d, C6H5-ortho,
2JPC = 10.9 Hz), 134.77 (s, C1), 135.65 (d, C6H5-ipso, 1JPC = 81.7 Hz),
138.64 (s, C2). 31P NMR: δ = 64.0 s. 77Se NMR: δ = 608s. IR (KBr) =
νas(PS2) 657 s, νs(PS2) 530 s cm–1.
Compounds 2–4 were prepared similarly.
Experimental Section
General: Solvents were dried by standard procedures and were freshly [2-(Et2NCH2)C6H4]SeSP(S)(OiPr)2 (2): From [2-(Et2NCH2)C6H4]2Se2
distilled prior to use. The diorganodiselenides [2-(R2NCH2)C6H4]2Se2 (0.390 g, 0.8 mmol) and [(iPrO)2P(S)S]2 (0.345 g, 0.8 mmol), as an or-
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Hypervalent Organoselenium(II) Compounds with Organophosphorus Ligands
Table 3. X-ray crystallographic data for 3 and 4.
3
4
Molecular formula
C25H30NPS2Se
518.55
C19H34NO2PS2Se
482.52
M
Temperature /K
Crystal size /mm
Crystal system
Space group
297(2)
297(2)
0.34 × 0.32 × 0.30
monoclinic
P21/n
0.31 × 0.28 × 0.26
monoclinic
P2(1)
Radiation /Å
Mo-Kα, 0.71073
Mo-Kα, 0.71073
Unit cell dimension
a /Å
10.118(9)
15.250(13)
16.711(14)
90.00
8.326(5)
16.722(9)
9.391(5)
90.00
b /Å
c /Å
α /°
β /°
93.956(14)
90.00
112.343(9)
90.00
γ /°
V /Å3
2572(4)
1209.3(11)
2
Z
4
Dcalc /g·cm–3
1.339
1.325
F(000)
1072
504
μ(Mo-Kα) /mm–1
θ Range for data collections /°
Reflections collected
Independent reflections
Max. and min. transmissions
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
Largest difference peak and hole /e·Å–3
1.697
1.804
1.81 to 25.00
11721
2.34 to 25.00
11708
4455 [R(int) = 0.0447]
0.6301 and 0.5962
4258 [R(int) = 0.0382]
0.6513 and 0.6047
Full-matrix least-squares on F2
4455 / 0 / 275
1.060
R1 = 0.0574,wR2 = 0.1191
R1 = 0.0729, wR2 = 0.1254
0.706 and –0.391
4258 / 1 / 243
1.039
R1 = 0.0377, wR2 = 0.0798
R1 = 0.0420, wR2 = 0.0814
0.289 and –0.322
ange oil. Yield: 0.573 g (78 %). C17H30NO2PS2Se (M = 454.48): calcd. C 47.29, H 7.10, N 2.90 %; found: C 47.38, H 7.29, N 3.02 %. 1H NMR:
C 44.93, H 6.65, N 3.08 %; found: C 45.12, H 6.48, N 3.15 %. 1H δ = 1.11 [d, 12 H, NCH(CH3)2, 3JHH = 6.6 Hz], 1.16 [d, 6 H, POCH(CH3)2,
3
3
NMR: δ = 1.03 (t, 6 H, NCH2CH3, JHH = 7.1 Hz), 1.16 [d, 6 H, 3JHH = 6.1 Hz], 1.27 [d, 6 H, POCH(CH3)2, JHH = 6.1 Hz], 3.16 [sept, 2
3
3
3
POCH(CH3)2, JHH = 5.9 Hz], 1.25 [d, 6 H, POCH(CH3)2, JHH
=
H, POCH(CH3)2, JHH = 6.6 Hz], 3.64 (s, 2 H, CH2N), 4.77 [sept, 2 H,
5.9 Hz], 2.66 (q, 4 H, NCH2CH3, JHH = 7.1 Hz), 3.69 (s, 2 H, CH2N), NCH(CH3)2, 3JHH = 6,1 Hz], 7.1 (m, 2 H, C6H4, H3,4), 7.18 (m, 1 H, C6H4,
4.75 [sept, 2 H, POCH(CH3)2, 3JHH = 6.0 Hz], 7.1 (m, 2 H, C6H4, H3,4), H5), 7.91 (d, 1 H, C6H4, H6). 13C NMR: δ = 20.57 [s, NCH(CH3)2], 23.34
3
7.16 (t, 1H C6H4, H5), 7.96 (d, 1 H, C6H4, H6, JHH = 7.9 Hz). 13C [d, POCH(CH3)2, JPC = 5.6 Hz], 23.69 [d, POCH(CH3)2, 3JPC = 4.2 Hz],
3
3
3
2
NMR: δ = 10.04 [s, NCH(CH3)2], 23.4 [d, POCH(CH3)2, JPC
=
49.33 (s, CH2N), 52.39 [s, NCH(CH3)2], 73.12 [d, POCH(CH3)2, JPC
=
3
5.6 Hz], 23.72 [d, POCH(CH3)2, JPC = 4.1 Hz], 44.52 (s, NCH2CH3), 6.7 Hz], 126.08 (s, C4), 127.28 (s, C3), 127.71 (s, C6), 130.03 (s, C5),
58.85 (s, CH2N), 72.8 [d, POCH(CH3)2, 2JPC = 6.8 Hz], 125.86 (s, C4), 134.67 (s, C1), 140.04 (s, C2). 31P NMR: δ = 86.2s. 77Se NMR: δ = 587s.
126.87 (s, C3), 127.95 (s, C6), 130.26 (s, C5), 134.96 (s, C1), 138.61 (s, IR (KBr) = νas(PS2) 655 s, νs(PS2) 531 s cm–1.
C2). 31P NMR: δ = 88.8 s. 77Se NMR: δ = 628 s.
[2-(iPr2NCH2)C6H4]SeSP(S)Ph2 (3): From [2-(iPr2NCH2)C6H4]2Se2
(0.301 g, 0.7 mmol) and [Ph2P(S)S]2 (0.345 g, 0.8 mmol), as a yellow
Acknowledgement
Financial support from National University Research Council of Ro-
mania (Research Project PNII-ID 2404/2008) is greatly appreciated.
E.D. is grateful for financial support from the European Community
(Erasmus Programme) and from the Region Haute-Normandie
(France). Special thanks to Prof. Konstantin Karaghiosoff for fruitful
discussions.
solid. Yield: 0.575 g (89 %). M.p. 106 °C. C25H30NPS2Se (M =
518.57): calcd. C 57.90, H 5.83, N 2.70 %; found: C 57.78, H 5.88, N
3
2.73 %. 1H NMR: δ = 1.02 (d, 12 H, NCH(CH3)2, JHH = 6.6 Hz),
3.04 (sept, 2 H, NCH(CH3)2, 3JHH = 6,6 Hz), 3.62 (s, 2 H, CH2N), 6.97
(m, 1 H, C6H4, H3), 7.02 (m, 2 H, C6H4, H4,5), 7.34 (m, 6 H, C6H5-
meta+para), 7.69 (m, 1 H, C6H4, H6), 7.93 (dd, 4 H, C6H5-ortho, 3JPH
=
3
13.8, JHH = 7.5 Hz). 13C NMR: δ = 20.49 [s, NCH(CH3)2], 49.32 (s,
CH2N), 52.02 [s, NCH(CH3)2], 126.01 (s, C4), 127.0 (s, C3), 127.57 (s,
C6), 128.03 (d, C6H5-meta, 3JPC = 13.05 Hz), 130.12 (s, C5), 131.24 (s,
References
3
1
br., C6H5-ortho + C5, JPC = 10.8 Hz), 131.64 (d, C6H5-ipso, JPC
=
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Received: April 5, 2011
Published Online: June 30, 2011
1360
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1355–1360