Organoselenium(II) complexes containing organophosphorus ligands. Crystal and molecular structure of PhSeSP(S)Ph2, [2-{MeN(CH2CH2)2NCH2}C6 H4]SeSP(S)R′2 (R′ = Ph, OPr<

Article abstract of DOI:10.1016/j.jorganchem.2008.12.011

Arylselenium(II) derivatives of dithiophosphorus ligands of type ArSeSP(S)R₂ [Ar = Ph, R = Ph (1), OPrⁱ (2); 2-[MeN(CH₂CH₂)₂NCH₂] C₆H₄, R = Ph (3), OPrⁱ (4)

Full text of DOI:10.1016/j.jorganchem.2008.12.011

Journal of Organometallic Chemistry 694 (2009) 1308–1316
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Organoselenium(II) complexes containing organophosphorus ligands.
Crystal and molecular structure of PhSeSP(S)Ph2,
[2-{MeN(CH2CH2)2NCH2}C6H4]SeSP(S)R02 (R0 = Ph, OPri) and
[2-{O(CH2CH2)2NCH2}C6H4]SeSP(S)(OPri)2
Anca Beleaga a, Monika Kulcsar a, Calin Deleanu b, Alina Nicolescu c, Cristian Silvestru a, Anca Silvestru a,
*
a Faculty of Chemistry and Chemical Engineering, ‘‘Babes-Bolyai” University, RO-400028 Cluj-Napoca, Romania
b National NMR Laboratory, Institute of Organic Chemistry, Romanian Academy, P.O. Box 35-98, RO-060023 Bucharest, Romania
c Group of Biospectroscopy, ‘‘Petru Poni” Institute of Macromolecular Chemistry, RO-700487 Iasi, Romania
a r t i c l e i n f o
a b s t r a c t
Arylselenium(II) derivatives of dithiophosphorus ligands of type ArSeSP(S)R2 [Ar = Ph, R = Ph (1), OPri (2);
2-[MeN(CH2CH2)2NCH2]C6H4, R = Ph (3), OPri (4); 2-[O(CH2CH2)2NCH2]C6H4, R = OPri (6)] were prepared
by redistribution reactions between Ar2Se2 and [R2P(S)S]2. The derivative [2-{O(CH2CH2)2NCH2}-
C6H4]SeSP(S)Ph2 (5) was obtained by the salt metathesis reaction between [2-{O(CH2CH2)2NCH2}C6H4]-
SeCl and NH4S2PPh2. The compounds were investigated by multinuclear (1H, 13C, 31P, 77Se) NMR and
infrared spectroscopy. The crystal and molecular structures of 1, 3, 4 and 6 were determined by sin-
gle-crystal X-ray diffraction. In compounds 3, 4 and 6 the N(1) atom is intramolecularly coordinated to
the selenium center, resulting in a T-shaped geometry (hypervalent 10-Se-3 species). The dithiophospho-
rus ligands act as anisobidentate in 1 and monodentate in 3, 4 and 6. Supramolecular architectures based
on intermolecular Sꢀ ꢀ ꢀH and Nꢀ ꢀ ꢀH contacts between molecular units are formed in the hypervalent
derivatives 3 and 4, while in the compounds 1 and 6 the molecules are associated into polymeric chains
through either Seꢀ ꢀ ꢀS or Oꢀ ꢀ ꢀH contacts, with no further inter-chain interactions.
Article history:
Received 15 October 2008
Received in revised form 3 December 2008
Accepted 5 December 2008
Available online 16 December 2008
Keywords:
Hypervalent organoselenium(II)
Dithiophosphorus ligands
Molecular structure
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
organochalcogen(II) complexes with dithio ligands (dio-
rganodithiocarbamates, diorganodithiophosphinates and tetra-
The chemistry of hypervalent organochalcogen derivatives con-
taining ArE moieties (Ar = organic group with pendant arms with
potential for N ? E intramolecular coordination, E = Se, Te) have
attracted continuous interest in last years due both to their
increased thermal and hydrolytic stability and their potential
applications [1–8]. Selenium compounds with 2-(diorganoami-
nomethyl)phenyl and related organic groups in which the nitrogen
atom is intramolecularly coordinated to the chalcogen center were
already used as catalysts in asymmetric synthesis [9–17], as anti-
oxidant reagents or enzyme mimics [1,18–21]. The tellurium ana-
logues were less investigated.
We have previously reported on the synthesis, solution behav-
ior and molecular structure of some chalcogen(I) and chalcogen(II)
derivatives containing organic groups with pendant arm contain-
ing nitrogen donor atoms, i.e. 2-(Me2NCH2)C6H4 [6,22,23],
2-[O(CH2CH2)2NCH2]C6H4 and 2-[MeN(CH2CH2)2NCH2]C6H4 [24].
The structural investigations on a series of these compounds, i.e.
organodithioimidodiphosphinates) revealed a T-shaped geometry
of the chalcogen (Se, Te) atom, due to the intramolecular N ? E
interaction [6,22–24].
We developed our previous studies on organoselenium dithio
complexes by using bulkier organic groups with additional donor
atoms in compounds containing dithiophosphorus ligands. It is
well known that this type of ligands usually involve both sulfur
atoms in coordination to a metal or a metalloid center, acting as
chelate or bridging units [25–30]. In the above mentioned com-
plexes the dithio ligands behave monodentate, only one sulfur
atom being involved in coordination to the selenium center
[6,23]. However, structural changes could arise due to the nature
of the C,N-organic group attached to selenium or when this is re-
placed by a phenyl group.
Here we report on the synthesis and spectroscopic characteriza-
tion of some new hypervalent organoselenium(II) derivatives con-
taining 1,1-dithiophosphinato or 1,1-dithiophosphato ligands, i.e.
[2-{E(CH2CH2)2NCH2}C6H4]SeSP(S)R2 [E = NMe, R = Ph (3), OPri
(4); E = O, R = Ph (5), OPri (6)]. In order to investigate the structural
modifications induced by a C,N-organic ligand vs. a phenyl group in
organoselenium(II) complexes we have also prepared and
diorganodichalcogenides,
organochalcogen(II)
halides
and
* Corresponding author. Tel.: +40 264 593833; fax: +40 264 590818.
E-mail address: ancas@chem.ubbcluj.ro (A. Silvestru).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.12.011

A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
1309
characterized the compounds PhSeSP(S)R2 [R = Ph (1), OPri (2)].
The crystal and molecular structures of compounds 1, 3, 4 and 6
were established by single-crystal X-ray diffraction.
([Ph2P(S)S]2, dP 69.6 ppm; [(PriO)2P(S)S]2, dP 81.6 ppm), as also ob-
served for the related [2-(Me2NCH2)C6H4]SeSP(S)R2 (R = Ph, dP
65.1 ppm; R = OPri, dP 90.0 ppm) [23].
The alkyl region in the room temperature NMR spectra of com-
pounds 3–6 exhibit, with respect to the pendant arm of the organic
group bound to selenium, 2-[E(CH2CH2)2NCH2]C6H4 (E = NMe, O), a
singlet resonance for the H7 protons and two broad resonances for
the H8,11 and H9,10 protons. A similar pattern was observed for the
R2Se2 starting materials [24] and suggests a considerable weakness
of the intramolecular N ? Se interaction which allows a fast con-
formational change of the six-membered morpholinyl or piperazi-
nyl ring. This contrasts with halides RSeX containing similar
organic groups for which the H8,11 and H9,10 protons became
non-equivalent as result of the stronger intramolecular N ? Se
interaction, i.e. pro-cis and pro-trans with respect to the position
of the selenium atom in relation to the E(CH2CH2)2N ring.
The 77Se resonances for compounds 3–6 (dSe range 552.1–
585.1 ppm) are downfield shifted with respect to those observed
for the phenylselenium derivatives 1 (dSe 486.3 ppm) and 2 (dSe
462.6 ppm) or the starting diselenides, [2-{E(CH2CH2)2NCH2}-
C6H4]2Se2 (E = NMe, dSe 425.4 ppm; E = O, dSe 425.4 ppm) [24]. They
are upfield shifted in comparison with the related [2-
{E(CH2CH2)2NCH2}C6H4]SeI (E = NMe, dSe 700.0 ppm, at +60 °C, in
CDCl3; E = O, dSe 702.0 ppm, at +26 °C, in CDCl3) [24], a behavior
consistent with the decreased deshielding of the selenium reso-
nances as the electronegativity of the attached substituent de-
creases [31].
2. Results and discussion
2.1. Preparation
The redistribution reactions between stoichiometric amounts of
the diorganodiselenides Ar2Se2 and the appropriate bis(diorgano-
thiophosphinyl)disulfane were carried out in dichloromethane
and afforded the compounds 1–4 and 6 in good yields, as yellow
crystalline solids, according to the following equation:
Ar2Se2 þ ½R2PðSÞSꢁ2 ! 2ArSeSPðSÞR2
Ar ¼ Ph; R ¼ Phð1Þ; OPri ð2Þ
ð1Þ
Ar ¼ 2-½MeNðCH2CH2Þ NCH2ꢁC6H4; R ¼ Ph ð3Þ; OPri ð4Þ
2
Ar ¼ 2-½OðCH2CH2Þ NCH2ꢁC6H4; R ¼ OPri ð6Þ
2
Compound 6 was obtained using a salt metathesis reaction be-
tween the corresponding organoselenium(II) chloride and ammo-
nium diphenyldithiophosphinate [Eq. (2)]:
ArSeCl þ NH4S2PPh2
!
ArSeSPðSÞPh2
ꢂNH4Cl
ð2Þ
Ar ¼ 2-½OðCH2CH2Þ2NCH2ꢁC6H4 ð5Þ
All compounds are stable in solid state for indefinite time, but
decomposition occurs in solution for the derivatives containing
an organic group with pendant arm. We have investigated the
reactions between Ar2Se2 and [R2P(S)S]2 directly in an NMR tube
for 1 month and we observed an advanced decomposition for com-
pounds 3, 4 and 6, while the NMR spectra of the Ph2Se2/[R2P(S)S]2
mixtures remained unchanged after the formation of the desired
compounds 1 and 2.
2.3. Infrared spectra
The IR spectra for compounds 1–6 exhibit strong absorption
bands in the regions 660–640 and 550–500 cmꢂ1 which were as-
signed to asymmetric and symmetric m(PS2) stretching vibrations
in the dithiophosphorus ligands attached to the organoselenium(II)
moieties.
2.2. NMR spectra
2.4. Crystal and molecular structure of PhSeS(S)PPh2 (1) and [2-
{E(CH2CH2)2NCH2}C6H4]SeS(S)PR02 [E = NMe, R0 = Ph (3), OPri (4);
E = O, R0 = OPri (6)]
The solution behavior of the new compounds 1–6 was investi-
gated by multinuclear (1H, 13C, 31P, 77Se) NMR spectroscopy, at
room temperature. 1H and 13C resonances were assigned using
2D NMR experiments, according to the numbering diagram de-
picted in Scheme 1.
In all compounds the proton and carbon resonances correspond-
ing to the organic groups attached to the phosphorus atom are split
into two components of equal intensity, due to the phosphorus–
proton and phosphorus–carbon couplings, respectively. The alkyl
region of the 1H NMR spectra of compounds 2, 4 and 6 exhibits a
pattern which is indicative for the diastereotopic nature of the
CH3 of the isopropoxy groups attached to phosphorus, i.e. two dou-
blet resonances for the HA and HB methyl protons, respectively.
The 31P NMR spectra of compounds 1–6 show singlet reso-
nances, shifted in comparison with the starting disulfanes
In order to reveal the changes produce by replacement of the
phenyl group attached to selenium by a potential C,N-chelating li-
gand and the competition for internal coordination between the
nitrogen from the pendant arm in the 2-{E(CH2CH2)2NCH2}C6H4
group and the sulfur atoms of a dithiophosphorus ligand moiety,
the molecular structures of compounds 1, 3, 4 and 6 were deter-
mined. Single-crystals suitable for X-ray diffraction studies were
obtained from a CH2Cl2/n-hexane (1:5, v/v) mixture for 1, 3 and
6, and from a CDCl3/n-hexane (1:4, v/v) mixture for 4, respectively.
Selected interatomic distances and angles for 1 are listed in
Table 1 and an ORTEP diagram is shown in Fig. 1a. The dith-
Table 1
Selected interatomic distances (Å) and angles (°) in 1.
Se(1)–C(1)
Se(1)–S(1)
P(1)–S(1)
P(1)–S(2)
C(1)–Se(1)-S(1)
C(1)–Se(1)ꢀ ꢀ ꢀS(2)
C(1)–Se(1)ꢀ ꢀ ꢀS(1a)a
S(1)–Se(1)ꢀ ꢀ ꢀS(2)
S(1)–Se(1)ꢀ ꢀ ꢀS(1a)a
S(2)–Se(1)ꢀ ꢀ ꢀS(1a)a
P(1)–S(1)–Se(1)
1.908(6)
2.205(2)
2.119(2)
1.935(3)
101.8(2)
122.2(2)
83.8(2)
63.00(6)
174.44(6)
113.85(5)
102.62(9)
Se(1)ꢀ ꢀ ꢀS(2)
3.795(2)
3.590(2)
1.814(6)
1.806(7)
114.71(12)
106.3(3)
107.1(2)
98.6(2)
114.0(2)
114.7(2)
62.62(8)
103.03(6)
Se(1)ꢀ ꢀ ꢀS(1a)a
P(1)–C(7)
P(1)–C(13)
S(1)–P(1)–S(2)
C(7)–P(1)–C(13)
S(1)–P(1)–C(7)
S(1)–P(1)–C(13)
S(2)–P(1)–C(7)
S(2)–P(1)–C(13)
P(1)–S(2)ꢀ ꢀ ꢀSe(1)
Se(1)ꢀ ꢀ ꢀS(1a)–Se(1a)a
a
Symmetry equivalent atoms (x, 0.5 ꢂ y, ꢂ0.5 + z) are given by ‘‘a”.
Scheme 1.

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A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
Fig. 1. ORTEP representation and atom numbering scheme for (a) 1; (b) the (R)-3 isomer; (c) the (R)-4 isomer; and (d) the (S)-6 isomer (30% and 20% probability for 1/3, and 4/
6, respectively; for compounds 4 and 6 hydrogen atoms are omitted for clarity).
iophosphinato ligand is primary connected to the selenium
through S(1) atom [Se(1)–S(1) 2.205(2) Å], resulting in a V-shaped
geometry of the covalent bonds around the selenium center, with a
C(1)–Se(1)–S(1) angle of 101.8(2)°, as also observed in the related
PhTeS(S)PPh2 [C–Te–S 99.2(1)°] [28]. The Se(1)–S(1) bond distance
of 2.205(2) Å is within the expected range for covalent selenium–
sulfur single bonds, but significant shorter than in [2-
(Me2NCH2)C6H4]SeS(S)PR2 [2.340(1) and 2.337(1) Å for R = Ph and
OPri, respectively], where a strong intramolecular Nꢀ ꢀ ꢀSe interac-
tion is established in trans to the Se–S bond [23].
A weak intramolecular Seꢀ ꢀ ꢀS interaction, shorter than the sum
of the van der Waals radii of the corresponding atoms, is also
established by the S(2) atom doubly bonded to phosphorus
Se(1)ꢀꢀꢀS(2) 3.795(2) Å; cf. the sums of the covalent and van der
Waals radii are
Rrcov(Se,S) 2.21 Å and RrvdW(Se,S) 3.85 Å [32].
The four-membered SeS2P ring is not planar, but folded along the
Table 2
Selected interatomic distances (Å) and angles (°) for compounds 3, 4 and 6.
3
4
6
Se(1)–C(1)
Se(1)–N(1)
Se(1)–S(1)
Se(1)ꢀ ꢀ ꢀS(2)a
1.943(4)
2.463(4)
2.2973(12)
4.037(1)
1.938(4)
2.529(3)
2.2769(12)
5.132(2)
1.943(7)
2.557(7)
2.276(2)
5.126(3)
P(1)–S(1)
P(1)–S(2)
2.0799(16)
1.9379(15)
2.0413(16)
1.9079(16)
2.056(3)
1.923(3)
N(1)–C(7)
N(1)–C(8)
N(1)–C(11)
1.465(5)
1.456(5)
1.466(5)
1.452(5)
1.453(5)
1.461(5)
1.462(12)
1.474(11)
1.467(10)
C(1)–Se(1)–S(1)
C(1)–Se(1)–N(1)
N(1)–Se(1)–S(1)
98.69(12)
77.8(1)
174.6(1)
98.29(12)
77.4(1)
173.5(7)
99.7(2)
75.2(3)
172.9(2)
P(1)–S(1)–Se(1)
97.99(5)
103.19(6)
102.01(10)
C(7)–N(1)–C(8)
C(7)–N(1)–C(11)
C(8)–N(1)–C(11)
Se(1)–N(1)–C(7)
Se(1)–N(1)–C(8)
Se(1)–N(1)–C(11)
112.6(4)
112.5(4)
110.8(3)
96.4(2)
111.4(2)
112.5(2)
112.5(3)
112.6(3)
110.5(3)
94.5(2)
113.5(2)
112.5(2)
114.1(9)
113.8(8)
109.1(7)
92.3(5)
112.4(5)
114.6(5)
S(1)–P(1)–S(2)
117.09(8)
107.15(18)
109.73(8)
98.2(3)
109.74(14)
99.8(3)
X(1)–P(1)–X(2)b
a
Non-bonding distance.
X(1) and X(2) are C(13) and C(24) for 3, O(1A) and O(2A) for 4, and O(2) and
Fig. 2. View of the chain polymer in the crystal of 1 based on intermolecular Seꢀ ꢀ ꢀS
contacts [symmetry equivalent atoms (x, 0.5 ꢂ y, ꢂ0.5 + z), (x, 0.5 ꢂ y, 0.5 + z) and
(x, y, 1 + z) are given by ‘‘a”, ‘‘b” and ‘‘c”, respectively].
b
O(3) for 6.

A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
1311
S(1)ꢀ ꢀ ꢀS(2) axis [dihedral angle of 48.2° between the P(1)/S(1)/S(2)
and Se(1)/S(1)/S(2) planes].
pattern of the dithiophosphinato ligand in 1 is bimetallic triconnec-
tive which contrast with that found in the related tellurium ana-
logue, PhTeS(S)PPh2, i.e. monodentate biconnective pattern (only
the sulfur atom single bonded to phosphorus is bridging two tellu-
rium atoms, while the sulfur atom doubly bonded to phosphorus is
not involved in interaction with the heavier chalcogen atoms) [28].
It was previously noted [6,24,34–39] that the intramolecular
coordination of the nitrogen atom to the metal center in com-
pounds containing 2-(R2NCH2)C6H4 groups induces planar chirality
due to the non-planar MC3N ring thus formed [the aromatic ring
In the crystal additional, even stronger, intermolecular Seꢀ ꢀ ꢀS
interactions [Se(1)ꢀꢀꢀS(1a) 3.590(2) Å] are established between
S(1) atom covalent bonded to selenium and the selenium center
of a neighboring molecule, thus resulting in a zig-zag chain polymer
(Fig. 2). However, the phosphorus–sulfur distances within the li-
gand moiety are consistent with single P–S and double P@S bonds
P(1)–S(1) 2.119(2), P(1)–S(2) 1.935(3) Å in 1; cf. P–S 2.077(1) and
P@S 1.954(1) Å in Ph2P(S)SH [33]. Thus, the overall coordination
Fig. 3. (a) View along the a axis of the chain polymer based on sulfur–hydrogen contacts between alternating S and R isomers; (b) View along the a axis of the double-layer
based on sulfur–hydrogen contacts in the crystal of 3 [only hydrogens involved in intermolecular contacts are shown; symmetry equivalent atoms (x, 1.5 ꢂ y, 0.5 + z), (x,
1.5 ꢂ y, ꢂ0.5 + z) and (1 ꢂ x, 1 ꢂ y, ꢂz) are given by ‘‘a”, ‘‘b” and ‘‘prime”, respectively].

1312
A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
and the nitrogen atom being the chiral plane and the pilot atom]
and therefore the compounds usually crystallize as racemates
[40]. Indeed, due to strong intramolecular SeꢀꢀꢀN interactions
[Se(1)–N(1) 2.463(4), 2.529(3) and 2.557(7) in 3, 4 and 6, respec-
The internal SeꢀꢀꢀN interactions are much stronger in 3, 4 and 6
than in the diselenides used as starting materials, i.e. [2-
{MeN(CH2CH2)2NCH2}C6H4]2Se2 [Seꢀ ꢀ ꢀN 3.135(3)/2.739(3) Å] and
[2-{O(CH2CH2)2NCH2}C6H4]2Se2 [Seꢀ ꢀ ꢀN 2.813(2)/2.825(3) Å] [24].
This behavior is consistent with the higher electronegativity of
the S(1) atom placed in trans to the N(1) atom in the N–Se–S frag-
ment [N(1)–Se(1)–S(1) 174.6(1), 173.5(7) and 172.9(2)° in 3, 4 and
6, respectively] and/or with the better leaving group character of
the dithiophosphorus anion compared to an ArSeꢂ anion due to
tively; cf.
Rrcov(Se,N) 1.87 Å, RrvdW(Se,N) 3.54 Å [32], compounds
3 and 4 crystallize as 1:1 mixtures of R and S isomers, while for
6 the crystal contains only the isomer S. Selected interatomic dis-
tances and angles are listed in Table 2 and the ORTEP diagrams
for (R)-3, (R)-4 and (S)-6 isomers are depicted in Fig. 1b–d.
Fig. 4. (a) View of the chain polymer of dimers based on nitrogen–hydrogen and sulfur–hydrogen contacts between R and S isomers; (b) View of the layer based on sulfur–
hydrogen contacts in the crystal of 4 [only hydrogens involved in intermolecular contacts are shown; symmetry equivalent atoms (2 ꢂ x, 1 ꢂ y, 1 ꢂ z), (x, ꢂ1 + y, z), (x, 1 + y, z),
(2 ꢂ x, ꢂy, 1 ꢂ z), (2 ꢂ x, 2 ꢂ y, ꢂ1 ꢂ z), (2 ꢂ x, 1 ꢂ y, 2 ꢂ z) and (2 ꢂ x, 2 ꢂ y, 2 ꢂ z) are given by ‘‘prime”, ‘‘a”, ‘‘b”, ‘‘prime a”, ‘‘prime b”, ‘‘prime c” and ‘‘prime d”, respectively].

A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
1313
better charge delocalization in the former. However the internal
Seꢀ ꢀ ꢀN interactions in the title compounds are weaker than in the
related [2-(Me2NCH2)C6H4]SeS(S)PR2 derivatives [Se–N 2.359(2)
and 2.397(2) Å for R = Ph and OPri, respectively] [23].
As in the parent diselenides [2-{E(CH2CH2)2NCH2}C6H4]2Se2
[24], the piperazinyl and morpholinyl rings exhibit a chair confor-
mation which prevents further intramolecular coordination of the
N(2) or O(1) atoms to the selenium centers in compounds 3, 4 and
6, and thus a (C,N,E)-monometallic triconnective pattern of the or-
ganic ligand.
The resulting T-shaped geometry of the (C,N)SeS core is similar
to those observed in the [2-(Me2NCH2)C6H4]SeS(S)PR2 derivatives.
The distortion of the coordination geometry is mainly due to con-
strains arising from the five-membered C3NSe chelate rings, partic-
ularly the C(1)–Se(1)–N(1) angle [77.8(1), 77.4(1) and 75.2(3)° in 3,
4 and 6, respectively]. The overall coordination geometry around
the selenium atom can be considered as distorted pseudo-trigonal
bipyramidal, with C(1) and the two lone pairs in equatorial posi-
tions (hypervalent 10-Se-3 species [41]).
In contrast to the phenylselenium derivative 1, the internal
Seꢀ ꢀ ꢀN interaction prevents any intra- or intermolecular secondary
interactions between selenium and the sulfur atoms of the organo-
phosphorus ligand. In compounds 4 [Se(1)ꢀ ꢀ ꢀS(2) 5.132(2) Å] and 6
[Se(1)ꢀ ꢀ ꢀS(2) 5.126(3) Å] the non-bonded sulfur atom is twisted as
far as possible from the selenium atom, while in 3 the S(2) atom is
brought closer to the selenium center at a distance [4.037(1) Å]
however longer than the sum of the van der Waals radii of the cor-
Fig. 5. View of the chain polymer based on sulfur–hydrogen contacts between S
isomers in the crystal of 6 [only hydrogens involved in intermolecular contacts are
shown; symmetry equivalent atoms (ꢂ0.5 + x, 0.5 ꢂ y, 2 ꢂ z) and (0.5 + x, 0.5 ꢂ y,
2 ꢂ z) are given by ‘‘a” and ‘‘b”, respectively].
responding atoms [cf.
RrvdW(Se,S) 3.85 Å] [32].
As result, the dithio ligands act monometallic monoconnective
in compounds 3, 4 and 6 and the phosphorus–sulfur distances
within the ligand moiety are consistent with single P–S and double
P@S bonds as was also observed in the related [2-(Me2NCH2)C6H4]-
SeS(S)PR2 derivatives [23]. The Se(1)–S(1) bond distances
[2.2973(12), 2.2769(12) and 2.276(2) Å in 3, 4 and 6, respectively]
are within the expected range for covalent selenium–sulfur single
bonds and of similar magnitude to those found in [2-
(Me2NCH2)C6H4]SeS(S)PR2 [Se(1)–S(1) 2.340(1) and 2.337(1) Å for
R = Ph and OPri, respectively] [23] They are longer than in 1
[2.205(2) Å] due to the trans effect of the internal Seꢀ ꢀ ꢀN interaction.
Table 3
X-ray crystal data and structure refinement for compounds 1, 3, 4 and 6
1
3
4
6
Empirical formula
Formula weight
T (K)
C18H15PS2Se
405.35
297(2)
C24H27N2PS2Se
517.53
297(2)
C18H31N2O2PS2Se
481.50
297(2)
C17H28NO3PS2Se
468.45
297(2)
k (Å)
0.71073
Monoclinic
P21/c
0.71073
Monoclinic
P21/c
0.71073
0.71073
Orthorhombic
P212121
Crystal system
Space group
Unit cell dimension
a (Å)
b (Å)
c (Å)
Triclinic
ꢀ
P1
8.9342(9)
24.866(2)
9.1142(9)
90
117.762(2)
90
1791.7(3)
4
1.503
12.8194(15)
11.4702(14)
16.784(2)
90
93.397(3)
90
2463.7(5)
4
1.395
8.872(2)
9.127(2)
15.181(3)
73.120(4)
89.930(4)
84.225(4)
1169.8(4)
2
8.6070(11)
14.2873(18)
18.288(2)
90
90
90
2248.9(5)
4
1.384
1.941
968
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (g cmꢂ3
)
1.367
1.866
500
Absorption coefficient (mmꢂ1
F(000)
)
2.411
816
1.772
1064
Crystal size (mm)
h Range for data collection (°)
Reflections collected
0.29 ꢃ 0.19 ꢃ 0.18
2.58–25.00
12890
0.44 ꢃ 0.23 ꢃ 0.14
2.15–25.00
12622
0.30 ꢃ 0.26 ꢃ 0.21
2.30–25.49
11347
0.38 ꢃ 0.24 ꢃ 0.21
1.81–25.00
16415
Independent reflections [Rint
]
3162 [0.0492]
3162/0/200
1.230
4329 [0.0462]
4329/0/272
1.136
4106 [0.0458]
4106/63/309
1.093
3962 [0.0873]
3962/0/231
1.094
Data/restraints/parameters
Goodness-of-fit on F2
Final R indicesa
R1
wR2
0.0840
0.1643
0.0565
0.1134
0.0494
0.1014
0.0740
0.1342
R indices (all data)
R1
0.1040
0.0739
0.0623
0.1000
wR2
0.1733
0.815 and ꢂ0.380
0.1199
0.568 and ꢂ0.435
0.1093
0.255 and ꢂ0.441
0.1438
0.469 and ꢂ0.473
Largest difference peak and hole (e Åꢂ3
)
a
I > 2r(I).

1314
A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
Even if no intermolecular interactions between heavy atoms are
Jasco FT/IR-615 instrument. Elemental analyses were performed
on a VarioEL analyzer.
observed for compounds 3, 4 and 6, different types of supramolec-
ular architectures are built in their crystals through S(2)ꢀ ꢀ ꢀH,
N(2)ꢀ ꢀ ꢀH and/or Omorpholinylꢀ ꢀ ꢀH contacts between the molecular
4.2. Preparation of phenylselenium(II) diphenyldithiophosphinate,
PhSeSP(S)Ph2 (1)
units [cf.
R
rvdW(S,H) ca. 3.05 Å;
R
rvdW(N,H) ca. 2.74 Å;
R
rvdW(O,H)
ca. 2.60 Å] [32]. Thus, in the crystal of 3 chains of alternating R and
S isomers are formed through Sꢀ ꢀ ꢀHaryl(P) contacts [S(2)ꢀ ꢀ ꢀH(20b)
2.74 Å] (Fig. 3a). Weaker inter-chain Sꢀ ꢀ ꢀHMeN-methylene-ring contacts
[S(2)ꢀ ꢀ ꢀH(10A0) 2.93 Å] result in a double-layer architecture in
which each R isomer is connected to four S isomers and vice-versa
(Fig. 3b). In the crystal of 4 not only S(2) atoms but also the N(2)
atoms are involved in contacts with hydrogens. Dimer units of R-
and S isomers are formed through NMeꢀ ꢀ ꢀHN-methylene-ring contacts
[N(2)ꢀ ꢀ ꢀH(11A0) 2.67 Å], which are further associated into a chain
polymer of dimers through inter-dimer Sꢀ ꢀ ꢀHMeN-methylene-ring con-
tacts [S(2)ꢀ ꢀ ꢀH(9Ab) 2.95 Å] (Fig. 4a). Even weaker Sꢀ ꢀ ꢀHaryl con-
tacts [S(2)ꢀ ꢀ ꢀH(50d) 3.01 Å] result in a layer of dimers (Fig. 4b),
with no further contacts between parallel layers.
Stoichiometric amounts of Ph2Se2 (1.0 g, 3.2 mmol) and
[(Ph2 P(S)S]2 (0.80 g, 3.2 mmol) in CHCl3 (30 ml) were stirred for
48 h. The solvent was removed in vacuum and the residual oil was
worked up with n-hexane (5 ml) when the title compound depos-
ited as a yellow powder. Yield: 1.87 g (72%). M.p. 58–60 °C. Anal.
Calc. for C18H15PS2Se: C, 53.33; H, 3.73. Found: C, 53.27; H, 3.65%.
3
1H NMR: d 7.12dd (2H, Se–C6H5-meta, JHH 7.6 Hz), 7.21t (1H, Se–
C6H5-para, 3JHH 7.4 Hz), 7.40 m (8H, Se–C6H5-ortho + P–C6H5-meta +
3
3
4
P–C6H5-para), 7.87ddd (4H, P–C6H5-ortho, JPH 14.1, JHH 7.0, JHH
1.6 Hz). 13C NMR: d 128.37d (P–C6H5-meta, JPC 13.2 Hz), 128.53
3
(Se–C6H5-para), 128.90 (Se–C6H5-meta), 130.19 (Se–C6H5-ipso),
2
4
131.84d (P–C6H5-ortho, JPC 10.9 Hz), 131.96d (P–C6H5-para, JPC
3.4 Hz), 132.93 (Se–C6H5-ortho, 2JSeC 12.1 Hz), 133.18d (P–C6H5-ipso,
1JPC 82.3 Hz). 31P NMR: d 66.2 (1JPC 82.7 Hz). 77Se NMR: d 486.3. IR
By contrast, in the crystal of 6 the S(2) atoms are not involved in
any intermolecular contacts but chain polymers are formed be-
tween S isomers through weak Omorpholinylꢀ ꢀ ꢀHmethylene contacts
[O(1)ꢀ ꢀ ꢀH(7Aa) 2.58 Å] (Fig. 5), with no further inter-chain
contacts.
(cmꢂ1):
mas(PS2) 652vs, ms(PS2) 517vs.
4.3. Preparation of phenylselenium(II) diisopropyldithiophosphate,
PhSeSP(S)(OPri)2 (2)
3. Conclusions
Prepared and worked up as for compound 1, from Ph2Se2 (0.5 g,
1.6 mmol) and [(PriO)2P(S)S]2 (0.68 g, 1.6 mmol) in CHCl3. Yield:
0.83 g (70%). M.p. 80–81 °C. Anal. Calc. for C12H19O2PS2Se: C,
39.02; H, 5.19. Found: C, 39.21; H, 5.02%. 1H NMR: d 1.16d [6HA,
New ArSeSP(S)R2 [Ar = Ph, R = Ph (1), OPri (2); 2-[MeN(CH2-
CH2)2NCH2]C6H4, R = Ph (3), OPri (4); 2-[O(CH2CH2)2NCH2]C6H4,
R = Ph (5), OPri (6)] were prepared and their structure was investi-
gated both in solution and in solid state. The NMR data suggest a
considerable weakness of the intramolecular N ? Se interaction
which allows a fast conformational change of the six-membered
piperazinyl or morpholinyl ring. In solid state the presence of a
C,N-organic group attached to selenium prevents any intra- or
intermolecular Seꢀ ꢀ ꢀS interactions, as observed for PhSeSP(S)Ph2
derivative. Compound 6 has crystallized in optically pure form.
Compounds 3, 4 and 6 exhibit a T-shaped coordination geometry,
i.e. (C,N)SeS core (hypervalent 10-Se-3 species). Supramolecular
architectures are built in solid state through intermolecular con-
tacts between hydrogen atoms and heavier electronegative (sulfur,
nitrogen and oxygen) atoms, i.e. layer networks for derivatives 3
and 4, and polymeric chains for compounds 1 and 6, with no fur-
ther inter-chain interactions.
3
3
P–O–CH(CH3)2, JHH 6.2 Hz], 1.32d [6HB, P–O–CH(CH3)2, JHH
3
3
6.1 Hz], 4.80dh (2H, P–O–CH(CH3)2, JPH 12.4, JHH 6.2 Hz), 7.28 m
(3H, Se–C6H5-meta + para), 7.70 m (2H, Se–C6H5-ortho). 31P NMR:
d 81.1. 77Se NMR: d 462.6. IR (cmꢂ1):
mas(PS2) 638vs, ms(PS2) 497s.
4.4. Preparation of [C,N-2-(N-methylpiperazinylmethyl)phenyl]-
selenium(II) diphenyldithiophosphinate, [2-{MeN(CH2CH2)2NCH2}-
C6H4]SeSP(S)Ph2 (3)
A
mixture of [2-{MeN(CH2CH2)2NCH2}C6H4]2Se2 (0.193 g,
0.36 mmol) and [(Ph2P(S)S]2 (0.179 g, 0.36 mmol) in CHCl3
(25 ml) was stirred for 48 h, at room temperature. The clear yellow
solution was then concentrated in vacuum and layered with n-hex-
ane. At low temperature (5 °C) the title compound deposited as a
yellow crystalline solid. Yield: 0.25 g (67%). M.p. 133 °C. Anal. Calc.
for C24H27N2PS2Se: C, 55.70; H, 5.26; N, 5.41. Found: C, 55.43; H,
5.34; N, 5.27%. 1H NMR:
H8,9,10,11), 3.42s (2H, H7), 6.96d (1H, H3, JHH 6.1 Hz), 7.06 m (2H,
d 2.24s (3H, N–CH3), 2.44br (8H,
4. Experimental
3
3
4.1. Materials and procedures
H4,5), 7.35s,br (6H, P–C6H5-meta + para), 7.84d (1H, H6, JHH
7.2 Hz), 7.95dd (4H, P–C6H5-ortho, JPH 12.7, JHH 6.6 Hz). 13C
3
3
All reactions were carried out under argon using standard
Schlenk techniques. Solvents were dried by standard procedures
and were freshly distilled prior to use. Ph2Se2 (Aldrich) was com-
mercially available. The other starting materials were prepared
according to the literature methods: [R2P(S)S]2 (R = Ph [42], OPri
[43]), Ph2PS2NH4 [44], R2Se2 (R = 2-[MeN(CH2CH2)2NCH2]C6H4, 2-
[O(CH2CH2)2NCH2]C6H4) [24]. Room temperature 1H, 13C and 31P
NMR spectra (in dried CDCl3), including 2D experiments, were re-
corded on a Bruker Avance DRX 300 instrument operating at
300.1, 75.5 and 121.4 MHz, respectively. The chemical shifts are
reported in ppm relative to the residual peak of solvent (ref.
CHCl3: 1H 7.26, 13C 77.0 ppm) and H3PO4 85%, respectively. The
77Se NMR spectra were obtained on a Bruker Avance DRX 400
instrument operating at 76.3 MHz. The 77Se NMR chemical shifts
are referred to external dimethylselenide (0.0 ppm) using as
external standard dimethyldiselenide (275.0 ppm) [45]. IR spectra
were recorded in the range 4000–400 cmꢂ1 as KBr pellets on a
NMR: d 45.58 (N–CH3), 51.66 (C8,11), 54.15 (C9,10), 62.39 (C7),
125.95 (C4), 127.00 (C3), 127.99d (P–C6H5-meta, JPC 12.7 Hz),
3
128.08 (C5), 130.57 (C6), 131.25 (P–C6H5-para), 131.57d (P–C6H5-
2
1
ortho, JPC 10.8 Hz), 134.24 (C2), 135.15d (P–C6H5-ipso, JPC
83.2 Hz), 137.68 (C1). 31P NMR: d 65.3. 77Se NMR: d 562.8. IR
(cmꢂ1):
mas(PS2) 656s, ms(PS2) 534vs.
4.5. Preparation of [C,N-2-(N-methylpiperazinylmethyl)phenyl]-
selenium(II) diisopropyldithiophosphate, [2-{MeN(CH2CH2)2NCH2}-
C6H4]SeSP(S)(OPri)2 (4)
Prepared and worked up as for compound 3, from [2-
{MeN(CH2CH2)2NCH2}C6H4]2Se2
(0.167 g,
0.31 mmol)
and
[(PriO)2P(S)S]2 (0.132 g, 0.31 mmol) in CHCl3. Yield: 0.23 g (77%).
M.p. 78–80 °C. Anal. Calc. for C18H31N2O2PS2Se: C, 44.90; H, 6.49;
N, 5.82. Found: C, 45.01; H, 6.64; N, 5.82%. 1H NMR: d 1.19d
3
3
[6HA, P–O–CH(CH3)2, JHH 6.2 Hz], 1.28d [6HB, P–O–CH(CH3)2, JHH

A. Beleaga et al. / Journal of Organometallic Chemistry 694 (2009) 1308–1316
1315
6.2 Hz], 2.31s (3H, N–CH3), 2.53, 2.61br [8H, H8,9,10,11], 3.61s (2H,
epoxy glue on cryoloops, and the data were collected at room tem-
perature (297 K). The structures were refined with anisotropic
thermal parameters. The hydrogen atoms were refined with a rid-
ing model and a mutual isotropic thermal parameter. The isopro-
poxy groups of compound 4 are disordered over two positions
and the atoms have been refined with a site occupancy of 57:43
(A/B). The Flack parameter for compound 6 is 0.038(18). In both
cases, the C–C bonds were restrained to 1.54 Å. The software pack-
age SHELX-97 was used for structure solving and refinement [46].
The drawings were created with the program DIAMOND [47].
3
3
H7), 4.78dh [2H, P–O–CH(CH3)2, JPH 12.2, JHH 6.1 Hz], 7.10 m
3
(2H, H3,4), 7.21 m (1H, H5), 7.98d (1H, H6, JHH 7.9 Hz). 13C NMR:
3
d
23.36d [CA, P–O–CH(CH3)2, JPC 5.7 Hz], 23.67d [CB, P–O–
3
CH(CH3)2, JPC 4.2 Hz], 45.83 (N–CH3), 51.88 (C8,11), 54.40 (C9,10),
2
62.69 (C7), 73.02d [P–O–CH(CH3)2, JPC 6.9 Hz], 125.96 (C4),
127.26 (C3), 128.14 (C5), 130.51 (C6), 134.63 (C2), 137.73 (C1). 31P
NMR: d 88.2. 77Se NMR: d 585.1. IR (cmꢂ1):
mas(PS2) 642vs, ms(PS2)
552s.
4.6. Preparation of [C,N-2-(N-morpholinylmethyl)phenyl]-
selenium(II)diphenyldithiophosphinate, [2-{O(CH2CH2)2NCH2}-
Acknowledgements
C6H4]SeSP(S)Ph2 (5)
This work was supported by the Romanian Ministry of Educa-
tion and Research (Grants CEx 11-55/2006 and CEx D11-16/2005).
Stoichiometric amounts of [2-{O(CH2CH2)2NCH2}C6H4]SeCl
(0.113 g, 0.39 mmol) and Ph2P(S)SNH4 (0.104 g, 0.39 mmol) were
stirred in CH2Cl2 (50 ml) for 12 h, at room temperature. The solu-
tion was concentrated in vacuum to minimum volume and then
kept at low temperature (ꢂ20°) for 24 h, when the title compound
deposited as a pale yellow solid. The compound was filtered off and
recrystallized from CH2Cl2/n-hexane (1:5, v/v). Yield: 0.17 g (85%).
M.p. 179 °C. Anal. Calc. for C23H24NOPS2Se: C, 54.76; H, 4.79; N,
2.78. Found: C, 54.48; H, 4.54; N, 2.62%. 1H NMR: d 2.42br (4H,
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jorganchem.2008.12.011.
References
H8,11), 3.38s (2H, H7), 3.55t (4H, H9,10
,
3JHH 4.2 Hz), 6.95d (1H, H3,
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3
3
7.82d (1H, H6, JHH 7.5 Hz), 7.92dd (4H, P–C6H5-ortho, JPH 13.9,
3JHH 7.0 Hz). 13C NMR: d 51.93 (C8,11), 62.66 (C7), 66.07 (C9,10),
3
125.86 (C4), 127.07 (C3), 127.82d (P–C6H5-meta, JPC 13.2 Hz),
127.92 (C5), 130.36 (C6), 131.15 (P–C6H5-para, JPC 2.8 Hz),
4
2
131.33d (P–C6H5-ortho, JPC 10.8 Hz), 133.91 (C1), 134.71d (P–
C6H5-ipso, JPC 82.9 Hz), 137.19 (C2). 31P NMR:
d
65.3 (1JPC
1
82.6 Hz). 77Se NMR: d 552.1.
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selenium(II)diisopropyldithiophosphate, [2-{O(CH2CH2)2NCH2}-
C6H4]SeSP(S)(OPri)2 (6)
Stoichiometric amounts of [2-{O(CH2CH2)2NCH2}C6H4]2Se2
(0.27 g, 0.53 mmol) and [(PriO)2P(S)S]2 (0.23 g, 0.53 mmol) were
stirred in CH2Cl2 (30 ml) for 12 h, at room temperature. The yellow
solution was concentrated in vacuum to minimum volume and
then kept at low temperature (ꢂ20 °C) for 24 h, when the title
compound deposited as a yellow solid. The compound was filtered
off and recrystallization from CH2Cl2/n-hexane (1:5, v/v) affords
isolation of the title compound as yellow crystals. Yield: 0.32 g
(63%). M.p. 137–138 °C. Anal. Calc. for C17H28NO3PS2Se: C, 43.59;
H, 6.02; N, 2.99. Found: C, 43.24; H, 5.83; N, 2.62%. 1H NMR: d
1.19d [6HA, P–O–CH(CH3)2, 3JHH 6.0 Hz], 1.28d [6HB, P–O–CH(CH3)2,
3JHH 6.0 Hz], 2.56br (4H, H8,11), 3.61s (2H, H7), 3.75t (4H, H9,10, 3JHH
3
3
4.2 Hz), 4.78dh [2H, P–O–CH(CH3)2, JPH 12.0, JHH 6.0 Hz], 7.12m
(2H, H3,4), 7.23 m (1H, H5), 7.99d (1H, H6, JHH 7.9 Hz). 13C NMR:
23.29d [CA, P–O–CH(CH3)2, JPC 5.6 Hz], 23.63d [CB, P–O–
CH(CH3)2, JPC 4.0 Hz], 52.28 (C8,11), 63.11 (C7), 66.48 (C9,10),
3
3
d
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3
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2
73.16d [P–O–CH(CH3)2, JPC 6.8 Hz], 126.07, 127.52 (C3,4), 128.26
(C5), 130.60 (C6), 134.56 (C1), 137.40 (C2). 31P NMR: d 87.7. 77Se
NMR: d 573.9. IR (cmꢂ1):
m
as(PS2) 644vs,
ms(PS2) 553s.
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4.8. X-ray structure determination
The details of crystal structure determination and refinement
for compounds PhSeSP(S)Ph2 (1), [2-{MeN(CH2CH2)2NCH2}C6H4]-
SeSP(S)Ph2 (3), [2-{MeN(CH2CH2)2NCH2}C6H4]SeSP(S)(OPri)2 (4)
and [2-{O(CH2CH2)2NCH2}C6H4]SeSP(S)(OPri)2 (6) are given in Ta-
ble 3. Data were collected with a Bruker SMART APEX diffractom-
eter by using graphite-monochromated Mo-K
(k = 0.71073 Å). For this purpose, block crystals were attached with
a
radiation
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