Organoselenium(II) and selenium(IV) compounds containing 2-(Me 2NCH2)C6H4 moieties: Solution behavior and solid state structure

Article abstract of DOI:10.1016/j.jorganchem.2005.02.052

The cleavage of the Se-Se bond in [2-(Me₂NCH₂)C ₆H₄]₂Se₂ (1) was achieved by treatment with SO₂Cl₂ (1:1 molar ratio) or elemental halogens to yield [2-(Me₂N

Full text of DOI:10.1016/j.jorganchem.2005.02.052

Journal of Organometallic Chemistry 690 (2005) 3217–3228
www.elsevier.com/locate/jorganchem
Organoselenium(II) and selenium(IV) compounds containing
-(Me NCH )C H moieties: solution behavior
and solid state structure
2
2
2
6 4
a
Monika Kulcsar , Anca Silvestru , Cristian Silvestru , John E. Drake ,
a
a,
b
*
b
Charles L.B. Macdonald , Michael E. Hursthouse , Mark E. Light
c
c
a
Faculty of Chemistry & Chemical Engineering, ‘‘Babes-Bolyai’’ University, RO-400028, Cluj-Napoca, Romania
b
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ont., Canada N9B 3P4
c
Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, United Kingdom
Received 5 February 2005; revised 11 February 2005; accepted 11 February 2005
Available online 17 May 2005
Dedicated to Professor Hans Joachim Breunig on the occasion of his 60th birthday
Abstract
The cleavage of the Se–Se bond in [2-(Me NCH )C H ] Se (1) was achieved by treatment with SO Cl (1:1 molar ratio) or
2
2
6
4 2
2
2
2
elemental halogens to yield [2-(Me
2
NCH
(5). [2-(Me
Me NCH )C H ]SeBr with Na[S CNR ] Æ nH O (R = Me, n = 2; R = Et, n = 3). The reaction of 3 with K[(SPMe )(SPPh )N]
2
)C
6
H
4
]SeX [X = Cl (2), Br (3), I (4)]. Oxidation of 1 with SO
2
Cl
2
(1:3 molar ratio) gave
[
2-(Me
2
NCH
2
6
)C H
4
]SeCl
3
2
NCH
2
)C ]SeS(S)CNR
6
H
4
2
[R = Me (6), Et (7)] were prepared by reacting [2-
(
2
2
6
4
2
2
2
2
2
resulted in isolation of [2-(Me NCH )C H ]Se–S–PMe @N–PPh @S (8). The compounds were characterized by solution NMR
2
2
6
4
2
2
1
13
31
77
spectroscopy ( H, C, P, Se, 2D experiments). The solid-state molecular structures of 2, 4–8 were established by single crystal
X-ray diffraction. All compounds are monomeric, with the N atom of the pendant CH NMe arm involved in a three-center-four-
2
2
electron Nꢀ ꢀ ꢀSe–X (X = halogen, S) bond. This results in a T-shaped coordination geometry for the Se(II) atom in 2, 4, 6–8. In 5, the
Se(IV) atom achieves a square pyramidal coordination in the mononuclear unit. Loosely connected dimers are formed through
˚
intermolecular Seꢀ ꢀ ꢀCl interactions (3.40 A); the overall coordination geometry being distorted octahedral. In all compounds hydro-
gen bonds involving halide or sulfur atoms generate supramolecular associations in crystals.
ꢀ
2005 Elsevier B.V. All rights reserved.
Keywords: Hypervalent organoselenium compounds; NMR studies; Crystal structures
1
. Introduction
ganobenzylamine and related ligands in which the nitro-
gen atom of the pendant arm is able to establish internal
Seꢀ ꢀ ꢀN interactions, the recent advances are due to their
potential applications, e.g. for asymmetric synthesis in
organic and organometallic chemistry [2–11], catalytic
antioxidant activity, enzyme mimics and chemothera-
peutic agents [12–16]. It was shown that such internal
interactions play an important role in chirality transfer
in asymmetric reactions. The stabilizing effect of internal
chelating groups in close proximity to selenium was also
The chemistry of organoselenium compounds stabi-
lized by the stereoelectronic effect of an intramolecular
Seꢀ ꢀ ꢀX (X = N, O, S) nonbonded interaction has been
the subject of increasing interest in recent years [1,2].
In particular, for Se compounds derived from N,N-dior-
*
Corresponding author. Tel.: +40 264 593833; fax: +40 264 590818.
E-mail address: cristi@chem.ubbcluj.ro (C. Silvestru).
0
022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.02.052

3218
M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
used for the isolation of exotic species such as the cova-
lent azide [2-(Me NCH )C H ]SeN [17] or the prepara-
able and the structural changes when the ‘‘bite’’ size of
potential chelating dithioligand is varied, [2-
(Me NCH )C H ]SeS(S)CNR [R = Me (6), Et (7)]
a
2
2
6
4
3
tion of monomeric metal chalcogenolates [18,19]. In
spite of this obvious interest only a few RSeX (X = hal-
ogen) derivatives containing ortho-selenurated benzyla-
mino and related moieties have been investigated so
far by single crystal X-ray diffraction, i.e. [2-
2
2
6
4
2
and [2-(Me NCH )C H ]Se–S–PMe @N–PPh @S (8)
2
2
6
4
2
2
were prepared. Their molecular structures were also
established by single-crystal X-ray diffraction and are
compared with those recently reported for [2-
i
(
Me NCH )C H ]SeBr [20], the adducts [2-(CyM-
2
(Me NCH )C H ]SeS(S)PR (R = Ph, OPr ) [28].
2
2
6
4
2
6
4
2
eNCH )C H ]SeX Æ HX (Cy = cyclohexyl, X = Cl, Br)
2
6
4
(
(
better described as ammonium salts of the type [{2-
+
CyMeHNCH )C H }SeX] [X] , which do not contain
ꢁ
2. Results and discussion
2
6
4
an intramolecular Seꢀ ꢀ ꢀN interaction) [21] and the cop-
per complex [[2-{2-(NC H CH CH ) NCH }C H ]-
6
2.1. Preparation
5
4
2
2 2
2
4
SeCl] (CuCl ) [22]. The electronic structure around
2
2 2
the selenium atom and the strength of the Seꢀ ꢀ ꢀN inter-
The organoselenium(II) halides, [2-(Me NCH )-
2 2
action in [2-(Me NCH )C H ]SeCl were also investi-
2
C H ]SeX [X = Cl (2), Br (3), I (4)] and organosele-
6 4
2
6
4
gated by computational methods at various basis set
levels [17,22,23]. On the other hand a check of the Cam-
bridge Structural Database (CSD) [24] for a CSeX3
nium(IV) trichloride, [2-(Me NCH )C H ]SeCl (5),
2 2 6 4 3
were prepared in good yields by the cleavage of the
Se–Se bond in [2-(Me NCH )C H ] Se (1) with elemen-
2
2
6
4 2
2
(
X = halogen) fragment revealed that the molecular
tal halogens or SO Cl (1:1 and 1:3 molar ratio), at
2 2
structure of only three organoselenium(IV) trichlorides
were so far reported, i.e. CF SeCl [25], 1,2-
room temperature, in carbon tetrachloride (Scheme 1).
Reactions of 3 with stoichiometric amounts of alkali me-
tal salts of the dithioligands afford the isolation of [2-
(Me NCH )C H ]SeS(S)CNR [R = Me (6), Et (7)]
3
3
i
C H (SeCl ) [26] and 3; 5-Pr -4-ðMe SiÞ N–C H SeCl
6
4
3 2
2
3
2
6
2
3
[
27].
2
2
6
4
2
Our interest in the investigation of hypervalent com-
pounds of main group elements led us to the synthesis of
2-(Me NCH )C H ]SeX [X = Cl (2), I (4)], for which
and [2-(Me NCH )C H ]Se–S–PMe @N–PPh @S (8).
2
2
6
4
2
2
Attempts to prepare the analogous [2-(Me NCH )-
C H ]Se–S–PPh @N–PPh @S (9) by metathesis reaction
2
2
[
2
2
6
4
6
4
2
2
the molecular structures are discussed herein, together
with that of the new organoselenium(IV) trichloride,
between 3 and K[(SPPh ) N] always resulted in an im-
2 2
pure yellow solid containing traces of the free dithioli-
gand, (SPPh ) NH (see Section 2.2), which indicates
[
2-(Me NCH )C H ]SeCl (5). It should be mentioned
3
2
2
6
4
2 2
that while this work was in progress the CIF files for
molecular structures of [2-(Me NCH )C H ]SeX
that the compound is quite sensitive to hydrolysis.
Compounds 2–8 can be recrystallized from CH Cl /n-
2
2
6
4
2
2
(
X = Cl, I) became available as supplementary material
hexane mixtures as stable, yellow, crystalline solids (ex-
cept compound 4, whose crystals are red). The trichlo-
ride 5 decomposes slowly in CDCl3 solution to the
monochloride 2 and elemental chlorine, as indicated
by NMR spectra.
for the work reported by Klap o¨ tke and Co., and the
structures were briefly discussed [17]. In order to inves-
tigate the competition for internal coordination to the
selenium centre when different donor atoms are avail-
Scheme 1.

M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
3219
2
.2. NMR spectra
The room-temperature NMR ( H, C) spectra of
for 2), in agreement with the increase of electronegativ-
ity with the number of chlorine atoms attached to the
chalcogen.
1
13
compounds 2–8 in CDCl3 solution are very similar
with respect to the organic ligand attached to sele-
nium, showing the expected resonances in the alkyl
and the aryl region (the assignment of the signals
was based on 2D experiments). In all cases the reso-
nances for the protons of the pendant CH NMe
In addition to the resonances for the organic ligand
1
13
attached to selenium, the H and C NMR spectra
for compounds 6 and 7 exhibit signals for nonequiva-
lent organic groups in the diorganodithiocarbamato
moiety. This behavior is consistent with the partial
double bond nature of the carbon–nitrogen bond
and the monodentate coordination pattern of the dith-
ioligand in solution.
2
2
arm appear as singlets in the region 2.30–3.00 ppm
for CH and 3.60–4.50 ppm for CH , respectively (cf.
3
2
PhCH NMe [20]: d 2.24 and 3.40 ppm, respectively).
The dichalcogenoimidodiphosphinato ligands of
0
2
2
ꢁ
This is consistent either with (i) the absence of an
intramolecular Seꢀ ꢀ ꢀN interaction; (ii) a fast process
involving several steps – dissociation–regeneration of
the internal Seꢀ ꢀ ꢀN interaction, with pyramidal inver-
sion at the nitrogen center, as proposed for analogous
type ½ðXPR
2
ÞðYPR ÞNꢂ ðX; Y ¼ O; S; SeÞ, are well
2
known versatile ligands able to adjust to various coordi-
nation geometries required by metal centers [30].
Compared with the restrictive ‘‘bites’’ in 1,1-dichalco-
genophosphorus ligands (e.g. dithiophosphates,
ꢁ ꢁ
[(RO) PS ] , dithiophosphinates, [R PS ] , or dithio-
2 2 2 2
ꢁ
carbamates, [R NCS ] ), the flexibility of the XPNPY
2 2
[
fast conformational change of the chelate five-
2-(CyMeNCH )C H ]SeX derivatives [23]; or (iii) a
2
6
4
membered SeC N ring [assuming a planar (C,N)SeX
3
skeleton allows for a considerably wider range of ‘‘bite’’
so that such ligands are particularly appropriate for the
investigation of the competition for internal coordina-
tion to the selenium center when different donor atoms
core] in solution, thus yielding averaged NMR reso-
nances. The spectra of compound
1
( H) and
4
compound 6 ( H, C) remained unchanged when re-
1
13
3
1
corded in DMSO-d solutions, so that no conclusion
6
are available. The P spectrum (in CDCl ) of the solid
3
concerning possible Seꢀ ꢀ ꢀN interaction could be drawn.
product (9) isolated from there action of 3 with
K[(SPPh ) N] exhibits two broad, singlet resonances in
7
The reported Se chemical shifts in CDCl solution
7
3
2 2
for [2-(Me NCH )C H ]SeX (d 1030, 987 and 818 ppm
a 1:1 intensity ratio (the sample was always contami-
nated with some free dithio acid, resulting in a residual
2
2
6
4
for X = Cl [17], Br and I [20]) are of the same magni-
tude as those found for [2-(CyMeNCH )C H ]SeX
3
1
P signal at d 58.3 ppm; cf. (SPPh ) NH [31]: d
2
6
4
2 2
derivatives (d 1051 and 1011 ppm for X = Cl and Br,
respectively) [23], for which the presence of the inter-
nal Seꢀ ꢀ ꢀN interaction in solution was well docu-
mented by multinuclear NMR studies. Therefore, it
might be concluded that such an internal Seꢀ ꢀ ꢀN inter-
action is also present in solution for compounds 2–4.
It should be noted that the Se resonances of the
RSeX derivatives [R = 2-(4,4-dimethyl-2-oxazoli-
nyl)phenyl], which are also stabilized by an internal
57.6 ppm). This is consistent with monodentate coordi-
nation of the ligand through only one of the sulfur
atoms to selenium and the formulation of compound 9
as [2-(Me NCH )C H ]Se–S–PPh @N–PPh @S with
2
3
2
6
4
2
2
1
the two
P resonances assigned to Ph P–S (d
2
30.9 ppm) and Ph P@S (d 43.6 ppm), respectively (cf.
2
7
7
MeS–PPh @N–PPh @S [32]:
d
30.9 (Ph P–S),
2
2
2
42.0 ppm (Ph P@S)). The solution behaviour of 9 is sim-
2
ilar to that found for the tellurium analogue, [2-
(Me NCH )C H ]Te–S–PPh @N–PPh @S
Seꢀ ꢀ ꢀN interaction [29], are strongly upfield shifted
[d
31.7
2
2
6
4
2
2
(
respectively) compared to those of [2-(Me NCH )-
d 855.9, 849.5, and 762.2 ppm for X = Cl, Br and I,
(Ph P–S), 41.9 ppm (Ph P@S)], for which the molecular
2
2
structure and the monodentate pattern of the dithioli-
gand in the solid state were also established by single-
crystal X-ray diffraction [33].
2
2
C H ]SeX, although they follow the same trend with
6 4
respect to the electronegativity of the halogen. This
behavior indicates that, in addition to the effect of
the halogen atom, the nature of the organic group at-
tached to selenium can exhibit a considerable effect on
When an asymmetric dithioimidodiphosphinato li-
gand is present as in the case of compound 8, two iso-
1
mers are possible, i.e. (a) or (b). The H and
13
C
7
7
the magnitude of the Se chemical shifts and this ef-
fect should be considered when comparisons are made
between NMR parameters observed for different series
of compounds.
NMR spectra of 8 (CDCl3 solution) exhibit the
resonances for the organic groups attached to the phos-
phorus atom, with the splitting pattern due to phospho-
rus–proton and phosphorus–carbon couplings, as
3
1
The increase in the oxidation state of the selenium
atom in [2-(Me NCH )C H ]SeCl (5) is reflected in
expected for only one isomer. The P spectrum contains
two resonances which were assigned to Me P-S (d
2
2
6
4
3
2
1
downfield shifts of H resonances for all types of pro-
3
1
40.8 ppm, d, J 8.3, J
71.1 Hz) and Ph P@S (d
PP
PC
2
1
3
tons in comparison with 2. In the C spectrum of 5 a
3
42.6 ppm, d, J 8.3, J 107.7 Hz) on the basis of
1
PP PC
1
the J coupling constants, thus being consistent with
the presence of isomer (a) in solution.
larger deshielding was observed for the C atom directly
1
PC
attached to selenium (d 148.72 ppm in 5 vs. 138.06 ppm

3220
M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
listed in Table 1. It was shown previously that intramo-
lecular coordination of the nitrogen atom to a metal
center in compounds containing a [2-(Me NCH )-
C H ]M moiety induces chirality at the metal center
2
2
6
4
[
35–38]. Indeed, the crystals of compounds 2, 4, and 5
contain 1:1 mixtures of R- and S-isomers [with the
C(1)–C(6) aromatic ring and the N(1) atom as chiral
plane and pilot atom, respectively] [39]. The ORTEP
diagrams for the (S)-2 and (R)-4 isomers are shown in
Fig. 1(a) and (b), while an ORTEP representation of
the dimer association found in the crystal of 5 (see sub-
sequent discussion) is depicted in Fig. 1(c).
7
The Se NMR spectra of organoselenium(II) deriva-
7
tives containing dithioligands contain only one reso-
nance thus indicating the presence of only one Se-
containing species in solution. The magnitude of the
Se chemical shifts, i.e. d 631.9 (6) and 579.9 ppm (8),
are similar to those observed for thiophenolato deriva-
7
7
tives [2-(Me NCH )C H ]SeSPh (d 562.3 ppm, in 1:1
2
2
6
4
CD OH–CDCl ) [15] or [2-(CyMeNCH )C H ]SeSPh
(
3
3
2
6
4
d 571.5 ppm, in CDCl ) [21]. The upfield shifts observed
3
for the thio derivatives 6–8 in comparison with the ha-
lides 2–4 are consistent with a decreased deshielding as
the electronegativity of the substituent on the Se atom
decreases [34].
2
C H ]SeX [X = Cl (2), I (4)] and [2-(Me NCH )-
.3. Crystal and molecular structure of [2-(Me NCH )-
2 2
6
4
2
2
C H ]SeCl (5)
6
4
3
Single crystals suitable for X-ray diffraction studies
were obtained from CH Cl /n-hexane for the halides 2,
2
2
4
, and 5. Selected interatomic distances and angles are
Table 1
Selected interatomic distances (A) and angles (ꢁ) in 2, 4 and 5
˚
2
(X = Cl)
4 (X = I)
5 (X = Cl)
Se(1)–C(1)
Se(1)–N(1)
Se(1)–X(1)
Se(1)–Cl(2)
Se(1)–Cl(3)
1.926(2)
2.137(2)
2.4757(7)
1.930(3)
2.167(3)
2.8227(4)
1.937(3)
2.276(2)
2.3459(9)
2.3610(9)
2.4349(9)
N(1)–C(7)
N(1)–C(8)
N(1)–C(9)
1.480(3)
1.478(3)
1.479(3)
1.484(4)
1.477(4)
1.479(4)
1.479(4)
1.481(4)
1.481(3)
N(1)–Se(1)–X(1)
Cl(2)–Se(1)–Cl(3)
C(1)–Se(1)–N(1)
C(1)–Se(1)–X(1)
C(1)–Se(1)–Cl(2)
C(1)–Se(1)–Cl(3)
N(1)–Se(1)–Cl(2)
N(1)–Se(1)–Cl(3)
Cl(1)–Se(1)–Cl(2)
Cl(1)–Se(1)–Cl(3)
175.97(5)
179.03(7)
174.71(6)
177.40(3)
80.1(1)
81.47(8)
94.59(7)
81.6(1)
97.53(9)
95.83(9)
91.55(8)
90.42(8)
93.40(6)
88.62(6)
90.02(4)
88.08(4)
C(7)–N(1)–C(8)
C(7)–N(1)–C(9)
C(8)–N(1)–C(9)
Se(1)–N(1)–C(7)
Se(1)–N(1)–C(8)
Se(1)–N(1)–C(9)
112.0(2)
111.7(2)
111.0(2)
103.2(1)
109.1(2)
109.5(1)
111.4(3)
112.2(3)
111.4(3)
103.4(2)
109.6(2)
108.4(2)
109.7(2)
113.3(2)
109.9(2)
102.4(2)
113.8(2)
107.7(2)
Fig. 1. ORTEP representation at 50% probability and atom number-
ing scheme for (a) the (S)-2 isomer; (b) the (R)-4 isomer; and (c) the
dimer association of (R)/(S) isomers in the crystal of 5 [symmetry
equivalent atoms (1 ꢁ x, 2 ꢁ y, 2 ꢁ z) are given by ‘‘prime’’].

M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
3221
For all three halides, the 2-(Me NCH )C H moiety
2
In the crystals of 2 and 4 the molecular units are sep-
arated by normal van der Waals distances between
heavy atoms [longer than the sums of the respective
2
6
4
acts as a (C,N)-ligand with the nitrogen atom very
strongly coordinated to the selenium centre trans to a
Se–halogen bond (cf. the sums of the covalent and van
P
P
˚
van der Waals radii
(Se,Cl) ca. 3.80 A, vdW(Se,I)
vdW
P
˚
˚
der Waals radii are
(Se,N) ca. 1.87 A and
ca. 4.15 A [40]]. This is in contrast to the [2-(4,4-di-
methyl-2-oxazolinyl)phenyl]SeX derivatives, the mole-
cules of which were found to form dimer associations
in the crystal, through weak intermolecular Seꢀ ꢀ ꢀX inter-
cov
P
˚
vdW(Se,N) ca. 3.54 A [40]). This results in a T-shaped
(C,N)SeX core (hypervalent 10-Se-3 species [41]) for
compounds 2 and 4 [N(1)–Se(1)–X(1) 175.97(5) and
˚
1
ativity of the halogen in the [2-(Me NCH )C H ]SeX
79.03(7)ꢁ, respectively]. The decrease in the electroneg-
actions [3.476(8), 3.556(9) and 3.752(2) A for X = Cl, Br,
I] [29]. A closer check of the crystal structures of 2 and 4
revealed several hydrogen bonding interactions resulting
in similar supramolecular arhitectures. Within a mole-
cule of [2-(Me NCH )C H ]SeX there is a short intra-
2
2
6
4
series does not strongly affect the strength of the internal
Seꢀ ꢀ ꢀN interaction [Se(1)–N(1) 2.137(2) (cf. 2.135(4)
˚
17]), 2.143(6) [20] and 2.167(3) (cf. 2.172(3) [17]) A for
[
2
2
6
4
˚
2
methyl-2-oxazolinyl)phenyl]SeX series [Se–N 2.052(2),
, 3, and 4], as was more evident in the [2-(4,4-di-
molecular Xꢀ ꢀ ꢀH contact: Cl(1)ꢀ ꢀ ꢀH(6) 2.73 A and
˚
I(1)ꢀ ꢀ ꢀH(6) 2.95 A [cf. sum of the respective van der
P
P
˚
.063(3) and 2.133(4) A for X = Cl, Br and I] [29]. The
˚
(Cl,H) ca. 3.0 A and
2
Waals radii is
(I,H)
vdW
vdW
˚
ca. 3.35 A] [40]. Dimer associations are formed between
linear arrangement of the Nꢀ ꢀ ꢀSe–X unit (3c–4e system)
results in the elongation of the Se–halogen bonds in
organoSe(II) halides stabilized by internal Seꢀ ꢀ ꢀN inter-
pairs of R- and S-isomers through intermolecular
0
˚
Xꢀ ꢀ ꢀH
contacts [Cl(1)ꢀ ꢀ ꢀH(8B ) 2.82 A and
˚
methyl
0
action. The Se–halogen bond lengths [Se(1)–X(1)
˚
I(1)ꢀ ꢀ ꢀH(8A ) 3.20 A] (Fig. 2(a)). Further inter-dimer
0
˚
methylene
2
.4757(7) A (cf. 2.471(2) [17]), 2.634(1) [20] and
˚
.8227(4) (cf. 2.8079(7) [17]) A in in 2, 3, and 4] are sim-
Xꢀ ꢀ ꢀH
contacts [Cl(1)ꢀ ꢀ ꢀH(7B c) 2.88 A and
˚
0
2
ilar to those found in the related [8-Me NC H ]SeX
I(1)ꢀ ꢀ ꢀH(7B c) 3.22 A] led to a layered structure in which
a dimer unit is connected to four neighboring dimers
(Fig. 2(b)). For compound 4 additional weak interdimer
2
10
6
[Se–X 2.429(2) and 2.7419(9) for X = Cl and I] [42]
or [2-(4,4-dimethyl-2-oxazolinyl)phenyl]SeX [Se–X
0
Iꢀ ꢀ ꢀH
contacts are established [I(1)ꢀ ꢀ ꢀH(9C d)
methyl
˚
3.18 A].
˚
.482(8), 2.6318(7) and 2.7773(7) A for X = Cl, Br and
2
I] [29]. They are considerably longer than observed for
The Se(1)–N(1) distance in the trichloride 5 is surpris-
˚
ingly slightly longer [2.276(2) A] than in 2, but still cor-
responds to a strong interaction. The Se–Cl bond
[
2
2,4,6-Me C H ]SeX [Se–X 2.186(1), 2.3331(8) and
3
˚
.529(1) A for X = Cl, Br [43] and I [44]].
6
2
Fig. 2. Hydrogen bonding in the crystal of 2: (a) dimer association of (R)-2/(S)-2 isomers [symmetry equivalent atoms (ꢁx, ꢁy, ꢁz) are given by
‘prime’’]; and (b) view along c axis of a layer network based on intermolecular hydrogen bonding [only hydrogens involved in intermolecular
‘
interactions are shown; symmetry equivalent atoms (ꢁ0.5 + x, 0.5 ꢁ y, ꢁz), (0.5 ꢁ x, 0.5 + y, z), (0.5 ꢁ x, ꢁ0.5 + y, z) and (ꢁ0.5 + x, ꢁ0.5 ꢁ y, ꢁz)
are given by ‘‘a’’, ‘‘prime b’’, ‘‘prime c’’ and ‘‘d’’].

3222
M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
Table 2
Selected interatomic distances (A) and angles (ꢁ) in 6, 7 and 8
˚
6
7
8
Se(1)–C(1)
Se(1)–N(1)
Se(1)–S(1)
1.929(2)
2.443(2)
2.2659(7)
1.941(5)
2.472(4)
2.247(1)
1.942(3)
2.439(3)
2.291(1)
N(1)–C(7)
N(1)–C(8)
N(1)–C(9)
1.455(3)
1.451(3)
1.469(3)
1.461(6)
1.449(6)
1.475(6)
1.442(5)
1.444(5)
1.458(6)
C(10)–S(1)
C(10)–S(2)
C(10)–N(2)
C(11)–N(2)
1.783(2)
1.660(2)
1.330(3)
1.467(4)
1.462(3)
1.797(5)
1.659(5)
1.342(6)
1.470(6)
1.470(6)
a
C(X)–N(2)
P(1)–S(1)
N(2)–P(1)
N(2)–P(2)
P(2)–S(2)
2.088(1)
1.567(3)
1.614(3)
1.964(1)
C(1)–Se(1)–N(1)
C(1)–Se(1)–S(1)
N(1)–Se(1)–S(1)
78.78(8)
100.17(7)
175.69(5)
77.0(2)
99.0(2)
173.3(1)
78.0(1)
96.6(1)
172.5(1)
Se(1)–S(1)–C(10)
106.46(8)
106.8(2)
S(1)–C(10)–S(2)
N(2)–C(10)–S(1)
N(2)–C(10)–S(2)
122.1(1)
113.8(2)
124.1(2)
122.2(3)
113.4(3)
124.4(4)
C(10)–N(2)–C(11)
C(10)–N(2)–C(X)
C(11)–N(2)–C(X)
120.8(2)
123.8(2)
115.4(2)
124.4(4)
120.2(4)
115.4(4)
Fig. 3. View of the polymeric association of dimers based on
intermolecular hydrogen bonding in the crystal of 5 [only hydrogens
involved in Clꢀ ꢀ ꢀH contacts are shown; symmetry equivalent atoms
C(7)–N(1)–C(8)
C(7)–N(1)–C(9)
C(8)–N(1)–C(9)
Se(1)–N(1)–C(7)
Se(1)–N(1)–C(8)
Se(1)–N(1)–C(9)
111.8(2)
113.5(2)
111.9(2)
100.8(1)
110.7(2)
107.4(2)
112.7(4)
111.4(4)
111.7(4)
98.6(3)
113.1(4)
111.7(4)
111.2(4)
97.5(2)
(
ꢁ1 + x, 1 + y, z) and (ꢁ1 + x, 3 ꢁ y, 2 ꢁ z) are given by ‘‘a’’ and
‘
‘prime a’’].
108.7(3)
113.1(3)
115.0(3)
107.6(3)
Se(1)–S(1)–P(1)
S(1)–P(1)–N(2)
P(1)–N(2)–P(2)
S(2)–P(2)–N(2)
a
98.65(4)
115.1(1)
137.1(2)
120.3(1)
distances are shorter than in 2 and are different (Table
), the shorter one corresponding to the Cl(1) atom trans
to the nitrogen. The coordination geometry around the
Se center is distorted square pyramidal, with the aro-
matic ipso carbon in apical position [N(1)–Se(1)–Cl(1)
1
C(X) = C(12) and C(13) for 6 and 7, respectively.
1
74.71(6)ꢁ, Cl(2)–Se(1)–Cl(3) 177.40(3)ꢁ]. Dimer associ-
ations between pairs of R- and S-isomers are formed
through weak intermolecular Seꢀ ꢀ ꢀCl interactions
are
short
inter-dimer
˚
Clꢀ ꢀ ꢀH
contacts
methyl
0
˚
Se(1)–Cl(2 ) 3.400(4) A] trans to the Se(1)–C(1) bond
[Cl(1)ꢀ ꢀ ꢀH(9Ca) 2.74 A] which result in a columnar
[
[
0
polymeric association of the dimers (Fig. 3).
Cl(2 )ꢀ ꢀ ꢀSe(1)–C(1) 171.0(1)ꢁ], with the internal Se–N
interactions placed in trans with respect to the planar
Se Cl ring thus formed (Fig. 1(c)). The overall coordi-
2.4. Crystal and molecular structure of [2-(Me NCH )-
2
2
2
2
nation geometry around selenium can be described as
distorted octahedral [(C,N)SeCl core, hypervalent 14-
C H ]SeS(S)CNR [R = Me (6), Et (7)] and
6
4
2
[2-(Me NCH )C H ]Se–S–PMe @N–PPh @S (8)
4
2
2
6
4
2
2
Se-6 species [41]]. Similar dimer associations based on
much stronger intermolecular Seꢀ ꢀ ꢀCl interactions are
found in the crystals of CF SeCl [folded Se Cl ring
Single crystals suitable for X-ray diffraction studies
were obtained from CH Cl /n-hexane for compounds
3
3
2
2
2
2
(
range 2.51(2)–2.75(2) A and cis Se–C bonds] [25] and
folding angle 154ꢁ), bridging Se–Cl distances in the
6–8 which contain a dithioligand. Selected interatomic
distances and angles are listed in Table 2. The crystals
of compounds 6 and 8 contain 1:1 mixtures of R- and
S-isomers, while for 7 the crystal contains only the iso-
mer R. The ORTEP diagrams for the (S)-6, (R)-7 and
(R)-8 isomers are shown in Fig. 4.
˚
i
3
bridging Se–Cl distances 2.587(2)–2.749(2) A and trans
; 5-Pr -4-ðMe SiÞ N–C H SeCl [planar Se Cl ring,
2
3
2
6
2
3
2
2
˚
Se–C bonds] [27]. In addition to the intramolecular
˚
Cl(1)ꢀ ꢀ ꢀH(6) interaction [2.66 A], in the crystal of 5 there

M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
3223
Fig. 5. Associations in the crystals of compounds 6–8 based on Sꢀ ꢀ ꢀH
contacts (only hydrogens involved in such contacts are shown):
(
a) double-chain polymer of (S)-6 isomers [symmetry equivalent atoms
Fig. 4. ORTEP representation at 40% probability and atom number-
ing scheme for (a) the (S)-6; (b) the (R)-7; and (c) the (R)-8-isomers.
(x, 1 + y, z), (ꢁ0.5 + x, 0.5 + y, 0.5 ꢁ z), (ꢁ0.5 + x, ꢁ0.5 + y, 0.5 ꢁ z)
and (x, ꢁ1 + y, z) are given by ‘‘a’’, ‘‘b’’, ‘‘c’’ and ‘‘d’’]; (b) single-chain
polymer of (R)-7 isomers [symmetry equivalent atoms (1 + x, y, z) and
(
(
ꢁ1 + x, y, z) are given by ‘‘a’’ and ‘‘b’’]; and (c) dimer association of
R)/(S)-8 isomers [symmetry equivalent atoms (ꢁx, ꢁy, 1 ꢁ z) are
As in the case of halides 2 and 4 described above, the
molecules of compounds 6–8 feature a T-shaped coordi-
nation environment of the selenium center [(C,N)SeS
core] due to an internal Seꢀ ꢀ ꢀN interaction trans to a
sulfur atom [Se(1)–N(1)/N(1)–Se(1)–S(1) 2.4433(19)
given by ‘‘prime’’].
172.47(8)ꢁ for 6, 7, and 8, respectively]. The increase of
the Se–N distances in the thio derivatives 6–8 reflects
the decreased electronegativity of the sulfur atom in
A˚ /175.69(5)ꢁ, 2.472(4) A/173.3(1)ꢁ and 2.439(3) A/
˚
˚

3224
M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
comparison to that of the halogens in 2 and 4. Internal
Seꢀ ꢀ ꢀN interactions of intermediate strengths were ob-
served in the [2-(Me NCH )C H ]SeS(S)PR derivatives
3. Conclusions
New organoselenium(II) compounds containing the
2-(Me NCH )C H moiety were prepared and their
2
2
6
4
2
i
˚
˚
[
2.359(2) A and 2.397(2) A for R = Ph and OPr , respec-
tively] [28].
Regardless of the magnitude of their ‘‘bite’’ size,
2
2
6
4
hypervalent nature was investigated both in solution
and in solid state. The molecular structure of the new
organoselenium(IV) trihalide [2-(Me NCH )C H ]SeCl
3
the dithioligands act as monodentate moieties in all
three of these compounds, being attached to the Se
center through only one sulfur atom. The Se(1)–S(1)
2
2
6
4
was also established by X-ray diffraction. The dithioli-
gands in [2-(Me NCH )C H ]SeS(S)CNR [R = Me,
2
2
6
4
2
˚
bond distances [2.2659(7), 2.247(1) and 2.2911(10) A
for 6, 7, and 8] are within the expected range for
Et] and [2-(Me NCH )C H ]Se–S–PMe @N–PPh @S
2
2
6
4
2
2
were found to act as monodentate units in both solution
and the solid state. In the solid state, compounds 2, 4–6,
and 8 crystallize as 1:1 mixtures of R- and S-isomers,
while for 7 the crystal contains only the isomer R. In
the crystals, a network of intermolecular Xꢀ ꢀ ꢀH contacts
(X = Cl, I, S) generates different supramolecular archi-
tectures, i.e. discrete dimers, polymeric chains or layer
structures.
covalent selenium–sulfur single bonds, but are
stronger than those observed for related [2-
˚
(
Me NCH )C H ]SeS(S)PR derivatives [2.3400(7) A
2 2 6 4 2
i
˚
and 2.3373(10) A for R = Ph and OPr , respectively]
28]. The second sulfur atom of the dithioligands is
[
not involved in any intermolecular interaction with
selenium atoms. However, due to the smaller ‘‘bite’’
of the dithiocarbamato moiety the S(2) atom is
brought closer to the selenium center [Se(1)ꢀ ꢀ ꢀS(2)
˚
.483(1) in 6, and 3.433(1) A in 7] than in the
3
dithioimidodiphosphinato derivative
8
.430(1) A; cf. the sums of the covalent and van der
[Se(1)ꢀ ꢀ ꢀS(2)
P
4. Experimental
˚
4
P
˚
(Se,S) ca. 2.21 A and vdW(Se,S)
Waals radii are
˚
4.1. Materials and procedures
cov
ca. 3.85 A [40]]. The monodentate nature of the dith-
ioligands in compounds 6–8 is also supported by the
differences in the carbon–sulfur bond lengths within
a dithiocarbamato moiety and the phosphorus–sulfur
All manipulations were carried out under vacuum
or argon by Schlenk techniques. Solvents were dried
and distilled prior to use. Selenium, N,N-dimethylben-
and phosphorus–nitrogen bond lengths in 8 (Table
˚
zylamine, butyllithium (15% in hexane), Na[S
CN-
2
2
) [cf. MeS–PPh @N–PPh @S [32]: P–S 2.071(1) A,
Me ] Æ 2H O and Na[S CNEt ] Æ 3H O were commer-
2
2
2
2
2
2
2
˚
˚
˚
P@S 1.954(1) A, P–N 1.610(2) A, P@N 1.562(2) A].
A short intramolecular S(1)ꢀ ꢀ ꢀH(6) contact, analo-
gous to the Cl(1)ꢀ ꢀ ꢀH(6) one observed for the halide spe-
cies 2 and 4, is also present within the molecules of the
cially available. The other starting materials were
prepared according to the literature methods: [2-
(Me
[20] and K[(SPMe
NCH
)C
H
]Li [45], [2-(Me
)(SPPh )N] [46]. Room-temperature
H and C NMR spectra for compounds 3–7 (in
dried CDCl ), including 2D experiments, were re-
NCH )C H ] Se (1)
2
2
6
4
2 2 6 4 2 2
2
2
1
13
˚
dithio derivatives 6–8 (2.73, 2.76, and 2.70 A for 6, 7,
and 8, respectively; cf. sum of the van der Waals radii
3
P
˚
(S,H) ca. 3.05 A [40]). The crystals of com-
is
corded on a BRUKER AVANCE DRX 400 instru-
ment operating at 400.2 and 100.6 MHz, respectively.
vdW
pounds 6–8 also feature associations of the molecular
units through weak intermolecular Sꢀ ꢀ ꢀH contacts. The
change in the nature of the organic group of the dithio-
carbamato moiety results in different chain polymeric
associations for 6 and 7. In the crystal of 6 there are par-
allel chains along the b axis built from R- and S-isomers,
1
The H and C NMR spectra for 2 and 8 (in dried
13
3
1
P
CDCl
) and 4 and 6 (in DMSO-d
), as well as
6
3
NMR spectrum of 8 were recorded at room tempera-
ture on a VARIAN GEMINI 300S instrument operat-
ing at 299.5, 75.4 and 121.4 MHz, respectively. The
chemical shifts are reported in ppm relative to the
respectively, through Sꢀ ꢀ ꢀH
contacts [S(2)ꢀ ꢀ ꢀ
methylene
1
13
˚
H(7Bd) 2.92 A]. Inter-chain Sꢀ ꢀ ꢀH
contacts
residual peak of solvent (ref. CHCl
3
:
H 7.26,
C
N-methyl
1
13
˚
[
S(2)ꢀ ꢀ ꢀH(9Ac) 2.96 A] result in pairs of (R,R) and
S,S) chains (Fig. 5(a)). In contrast to 6, in the case of
, a methyl proton of an ethyl group is involved in the
77.0 ppm; DMSO-d
PO 85%, respectively. The Se spectra were ob-
tained at 57.2 MHz, in CDCl on a VARIAN MER-
6
:
H 2.50, C 39.43 ppm) and
7
7
(
7
H
3
4
3
˚
Sꢀ ꢀ ꢀH contact [S(2)ꢀ ꢀ ꢀH(12Ba) 3.00 A] which results in
chains built from R-isomers; there are no further inter-
chain Sꢀ ꢀ ꢀH contacts shorter than the corresponding
sum of the van der Waals radii (Fig. 5(b)).
CURY 300BB spectrometer using diphenyl diselenide
(80 ꢁC) as external standards. Chemical shifts are re-
7
7
ported relative to dimethyl selenide ( Se) (0 ppm) by
assuming that the resonance of the standard is at
460 ppm [47]. Abbreviations used in multiplicities
are: s, singlet; d, doublet; dd, doublet of doublets;
ddd, doublet of doublet of doublets; t, triplet; q, quar-
tet; m, multiplet.
Discrete dimer associations are present in the crystal
of 8. They are formed between pairs of R- and S-isomers
through
[
intermolecular
0
Sꢀ ꢀ ꢀHP-methyl
contacts
˚
S(2)ꢀ ꢀ ꢀH(11A ) 2.93 A] (Fig. 5(c)).

M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
3225
4.2. Preparation of [2-(dimethylaminomethyl)phenyl]-
selenium(II) chloride, [2-(Me NCH )C H ]SeCl (2)
sulfurylchloride (0.31 g, 2.34 mmol) in 40 ml carbon tet-
rachloride. The reaction mixture was stirred at room
temperature for 2 h and the deposited solid was filtered
off and washed with hexane. Its recrystallization from
CH Cl /n-hexane (1:5, v/v) gave 5 as yellow crystals.
2
2
6
4
A solution of 1 (0.85 g, 2.0 mmol) in 50 ml carbon tet-
rachloride was treated dropwise with a solution of
sulfurylchloride (0.27 g, 2.0 mmol) in 40 ml carbon tet-
rachloride. The reaction mixture was stirred at room
temperature for additional 2 h, then the resulting solid
was filtered off and washed with hexane. It was recrystal-
lized from CH Cl /n-hexane (1:5, v/v) to give 2 as pale
2
2
Yield: 0.44 g (89%). M.p. 120–122 ꢁC. Anal. Found: C,
33.54; H, 3.62; N, 4.12. Calc. for C H Cl NSe: C,
1
9
12
3
33.83; H, 3.79; N, 4.38%. H NMR: d 2.99s (6H, N–
CH ), 4.49s (2H, –CH –), 7.31d (1H, H , JHH 7.3
3
3
2
3
3
Hz), 7.53dd (1H, H , J
3
7.5, J
7.5 Hz), 7.59dd
2
2
4
HH
HH
3
(1H, H , J
3
7.5, J
3
7.9 Hz), 8.57d (1H, H , J
yellow crystals. Yield: 0.7 g (71%). M.p. 111–113 ꢁC
5
HH
HH
6
HH
1
13
(
CH ), 4.02s (2H, –CH –), 7.13d (1H, H ,
lit. 118–121 ꢁC, dec. [17]). H NMR: d 2.79s (6H, N–
8.1 Hz). C NMR: d 48.20 (N–CH ), 63.96 (–CH –),
3 2
3
J
.2 Hz), 7.19dd (1H, H , JHH 7.2, JHH 7.2 Hz),
126.83 (C ), 128.90 (C ), 130.59 (C ), 132.10 (C ),
5
3
2
3
HH
3
6
4
3
3
7
137.22 (C ), 148.72 (C ).
1
4
2
3
.33dd (1H, H , J
3
7.4, J
7
H , J
7.4 Hz), 8.11d (1H,
HH
5
HH
13
3
7.9 Hz). C NMR: d 47.29 (N–CH ), 66.16
4.6. Preparation of [2-(dimethylaminomethyl)phenyl]-
selenium(II) dimethyldithiocarbamate, [2-(Me NCH )-
6
HH
3
(
(
–CH –), 125.09 (C ), 126.20 (C ), 129.16, 129.20
2 3 4
2
2
C5,6), 134.16 (C ), 138.06 (C ).
2
C H ]SeS(S)CNMe (6)
6 4 2
1
A mixture of 3 (0.44 g, 1.5 mmol) and Na[S CN-
2
4
.3. Preparation of [2-(dimethylaminomethyl)phenyl]-
selenium(II) bromide, [2-(Me NCH )C H ]SeBr (3)
Me ] Æ 2H O (0.26 g, 1.45 mmol) in 25 ml anhydrous
2
2
2
2
6
4
CH Cl was stirred at room temperature for 12 h. The
2
2
reaction mixture was filtered to remove NaBr and the
clear yellow filtrate was concentrated in vacuo until a
yellow solid deposited. The solid was filtered off and
Prepared and worked up as for compound 2, from 1
1.00 g, 2.34 mmol) and Br (0.37 g, 2.34 mmol) in car-
(
2
bon tetrachloride. Yield: 1.12 g (81%). M.p. 149 ꢁC
recrystallization from CH Cl /n-hexane (1:5, v/v) affords
2
1
2
(
lit. 149 ꢁC, dec. [20]). H NMR: d 2.76s (6H, N–CH ),
3
yellow crystals of 6. Yield: 0.3 g (62%). M.p. 76–78 ꢁC.
Anal. Found: C, 42.94; H, 5.27; N, 8.23. Calc. for
3
3
7
.97s (2H, –CH –), 7.09d (1H, H ,
J
7.4 Hz),
HH
2
3
3
3
.19dd (1H, H , J
7.4, J 7.4 Hz), 7.30dd (1H,
HH
1
C H N S Se: C, 43.24; H, 5.44; N, 8.40%. H NMR
4
HH
3
3
3
12 18
2 2
H ,
5
J
7.4, JHH 7.4 Hz), 8.13d (1H, H6, JHH
HH
(
CDCl ): d 2.39s (6H, N–CH ), 3.55s [3H, (S C)N–
1
3
3 3 2
8
1
1
.0 Hz). C NMR: d 47.05 (N–CH ), 66.00 (–CH –),
3 2
CH (A)], 3.63s [3H, (S C)N–CH (B)], 3.67s (2H, –
7.3,
3
2
3
25.23 (C ), 126.34 (C ), 129.20 (C ), 131.26 (C ),
34.69 (C ), 135.92 (C ).
3
CH –), 7.10m (2H, H ), 7.18ddd (1H, H , J
3
4
5
6
2
3,4
5
HH
2
1
3
4
JHH 7.3, J
3
2.0 Hz), 7.69d (1H, H , J
7.7 Hz).
HH
HH
6
1
H NMR (DMSO-d ): d 2.32s (6H, N–CH ), 3.40s
6
3
[
3H, (S C)N–CH (A)], 3.42s [3H, (S C)N–CH (B)],
2 3 2 3
4
.4. Preparation of [2-(dimethylaminomethyl)phenyl]-
selenium(II) iodide, [2-(Me NCH )C H ]SeI (4)
3
3
.67s (2H, –CH –), 7.17m (3H, H3-5), 7.54d (1H, H6,
2
13
2
2
6
4
JHH 7.4 Hz). C NMR (CDCl ): d 42.88 [(S C)N–
3
2
CH3 (A)], 43.86 (N–CH ), 46.67 [(S C)N–CH (B)],
64.01 (–CH –), 125.89, 127.03 (C3,4), 128.13 (C5),
3
2
3
Prepared and worked up as for compound 2, from
(0.62 g, 1.4 mmol) and I (0.37 g, 1.4 mmol) in car-
2
1
2
1
29.66 (C ), 136.22 (C ), 138.45 (C ), 198.24 [(S C)N–
2
6
2
1
bon tetrachloride. Yield: 0.8 g (81%). M.p. 148 ꢁC
1
3
1
CH3]. C NMR (DMSO-d ): d 42.63 [(S C)N–CH
6 2 3
(
N–CH ), 3.79s (2H, –CH –), 7.03d (1H, H , JHH
lit. 152 ꢁC [20]). H NMR (CDCl ): d 2.63s (6H,
3
3
(A)], 43.50 (N–CH ), 46.08 [(S C)N–CH (B)], 63.04
3 2 3
3
2
3
3
.9 Hz), 7.23m (2H, H ,5), 8.07d (1H, H6, JHH
(–CH –), 125.94, 127.28 (C ), 127.91 (C ), 129.01
2 3,4 5
6
8
4
1
(C ), 135.61 (C ), 138.42 (C ), 195.81 [(S C)N–CH ].
3
6
2
1
2
.0 Hz). H NMR (DMSO-d ): d 2.80s (6H, N–
6
7
7
Se NMR (CDCl ): d 631.9.
3
CH ), 4.12s (2H, –CH –), 7.28m (3H, H3-5), 7.95m
2
3
1
3
(
6
1
1H, H6).
C NMR (CDCl ): d 46.06 (N–CH ),
3
3
4.7. Preparation of [2-(dimethylaminomethyl)phenyl]
selenium(II) diethyldithiocarbamate, [2-(Me NCH )-
6.24 (–CH –), 125.63 (C ), 126.40 (C ), 129.15 (C ),
2 3 4 5
2
2
31.95 (C ), 135.46 (C ), 136.12 (C ).
2
1
6
C H ]SeS(S)CNEt (7)
6
4
2
4.5. Preparation of [2-(dimethylaminomethyl)phenyl]-
selenium(IV) trichloride, [2-(Me NCH )C H ]SeCl
A mixture of 3 (0.40 g, 1.36 mmol) and Na[S CNE-
2
t ] Æ 3H O (0.31 g, 1.38 mmol) in 25 ml anhydrous
2 2
2
2
6
4
3
(
5)
CH Cl was stirred at room temperature for 12 h. The
2 2
reaction mixture was filtered to remove NaBr and the
clear yellowish filtrate was concentrated in vacuo until
a yellowish solid deposited. The product was separated
A solution of 1 (0.33 g, 0.77 mmol) in 50 ml carbon
tetrachloride was treated dropwise with a solution of

Table 3
X-ray crystal data and structure refinement for compounds 2, 4–8
2
4
5
6
7
8
Empirical formula
Formula weight
T (K)
C
248.61
9
H
12ClNSe
C
340.06
9
H
12INSe
C
319.51
9
H
12Cl
3
NSe
C
12
H
18
N
2
S
2
Se
C
14
H
22
N
2
S
2
Se
C
23 28 2 2 2
H N P S Se
333.36
297(2)
361.42
120(2)
537.49
297(2)
0.71073
100(2)
100(2)
297(2)
0.71073
Triclinic
˚
k (A)
Crystal system
Space group
0.71073
Orthorhombic
Pbca
0.71073
Orthorhombic
Pbca
0.71073
Monoclinic
P2 /n
0.71073
Orthorhombic
P2
Orthorhombic
ꢀ
P1
1
1
2
1
2
1
Pbca
Unit cell dimensions
˚
a (A)
˚
7.6313(6)
10.8436(8)
23.539(2)
8.1066(4)
10.900(1)
23.585(1)
7.212(18)
7.236(2)
12.533(3)
80.732(4)
76.633(4)
74.151(4)
608.8(3)
2
8.440(12)
8.927(1)
19.368(3)
7.873(5)
8.484(1)
24.935(2)
9.166(12)
18.450(2)
30.212(4)
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90.047(2)
˚
3
Volume (A )
1947.8(3)
8
1.696
2084.0(2)
8
2.168
1459.3(4)
4
1665.4(2)
4
1.441
5109.2(12)
8
Z
ꢁ3
D
calc (g cm
)
1.743
3.704
316
1.517
2.840
680
1.398
1.772
2208
ꢁ1
Absorption coefficient (mm
F(000)
Crystal size (mm)
)
4.074
992
6.515
1280
2.495
744
0.50 · 0.50 · 0.45
3.18 to 27.54
17037
0.40 · 0.40 · 0.30
3.05 to 27.49
18795
0.32 · 0.20 · 0.13
1.68 to 26.37
4896
0.42 · 0.28 · 0.25
2.10 to 26.37
11312
0.02 · 0.02 · 0.01
3.06 to 27.47
4500
0.32 · 0.28 · 0.12
2.21 to 26.34
38719
h range for data collection (ꢁ)
Reflections collected
Independent reflections
Data/restraints/parameters
2236 [Rint = 0.0358]
2236/0/111
1.057
2398 [Rint = 0.0288]
2398/0/111
1.077
2443 [Rint = 0.0186]
2443/0/129
1.055
2981 [Rint = 0.0253]
2981/0/158
1.061
2579 [Rint = 0.0440]
2579/0/176
1.045
5213 [Rint = 0.0668]
5213/0/275
1.113
2
Goodness-of-fit on F
a
Final R indices
R
1
0.0279
0.0665
0.0298
0.0714
0.0283
0.0719
0.0288
0.0714
0.0368
0.0852
0.0507
0.1000
wR
2
R indices (all data)
R
1
0.0402
0.0719
0.0331
0.0732
0.0318
0.0736
0.0363
0.0747
0.0469
0.0889
0.0702
0.1067
wR
Extinction coefficient
Largest difference peak and hole (e A
2
ꢁ0.002(12)
0.681 and ꢁ0.559
˚
ꢁ3
)
0.733 and ꢁ0.390
2.919 and ꢁ0.406
0.676 and ꢁ0.446
0.355 and ꢁ0.19
0.439 and ꢁ0.404
a
2
2
F > 4r(F ) for 2, 4 and 7, and [I > 2r(I)] for 5, 6 and 8, respectively.

M. Kulcsar et al. / Journal of Organometallic Chemistry 690 (2005) 3217–3228
3227
by filtration and recrystallized from CH Cl /n-hexane
2
glass fibres (2, 4, and 7) and cryoloops (5, 6, and 8),
respectively. For 2, 4–6, and 8, a hemisphere of data
were collected on a Bruker APEX CCD diffractometer
using a counting time of 20 s (2, 4) or 10 s (5, 6, and
8) per frame. For 7 the data were collected on an Enraf
Nonius KappaCCD area detector diffractometer, with u
and x scans chosen to give a complete asymmetric unit.
Data reduction was performed using the SAINT [48] (for
2, 4–6, and 8) and DENZO [49] (for 7) software and the
data were corrected for Lorentz, polarization and
absorption effects using the SAINT and SADABS programs.
Cell refinement gave cell constants corresponding to
orthorhombic (for 2, 4, 7, and 8), triclinic (for 5)
and monoclinic (for 6) cells whose dimensions are
given in Table 3 along with other experimental
parameters.
2
(
1:5, v/v) to give 7 as a pale yellow solid. Yield: 0.3 g
(
N, 7.58. Calc. for C H N S Se: C, 46.53; H, 6.14; N,
61%). M.p. 68–70 ꢁC. Anal. Found: C, 46.37; H, 5.91;
1
4
22
2 2
1
3
7
6
2
.75%. H NMR: d 1.30t [3H, N–CH CH (A), J
2 3 HH
3
.7 Hz], 1.36t [3H, N–CH CH3 (B), JHH 6.7 Hz],
2
.38s (6H, N–CH ), 3.66s (2H, –CH –), 3.95q [2H, N–
3
2
3
CH CH (B), JHH 6.8 Hz], 4.11q (2H, N–CH CH
2
2
3
3
3
A), J
(
3
6.8 Hz), 7.08m (2H, H ), 7.18ddd (1H, H ,
3,4
HH
5
3
JHH 8.0, J
4
8.0, J
3
2.0 Hz), 7.70d (1H, H , J
HH 6 HH
HH
1
3
7
.9 Hz). C NMR: d 11.60 [N–CH CH (A)], 13.02
2 3
[
N–CH CH (B)], 43.81 (N–CH ), 47.77 [N–CH CH
2 3 3 2 3
(
B)], 50.72 [N–CH CH (A)], 64.01 (–CH –), 125.79,
2 3 2
1
26.98 (C3,4), 128.04 (C ), 129.68 (C ), 136.32 (C ),
6
5
2
1
38.48 (C ), 196.48 [(S C)N–CH CH ].
1
2
2
3
4
.8. Preparation of [2-(dimethylaminomethyl)-
0
The structures were solved by direct methods [50] and
refined using the WINGX (2, 4, and 7) [51] and SHELXTL (5,
6, and 8) [52] versions of SHELX-97 [53]. All of the non-
hydrogen atoms were treated anisotropically. Hydrogen
atoms were included in idealized positions with isotropic
thermal parameters set at 1.2 times that of the carbon
atom to which they were attached. The final cycle of
full-matrix least-squares refinement converged (largest
parameter shift was 0.001 times its e.s.d.). The drawings
were created with the DIAMOND program [54].
0
phenyl]selenium(II) P, P-dimethyl-P ,P -diphenyl-
dithiodiphosphinate, [2-(Me NCH )C H ]Se–S–
2
2
6
4
PMe @N–PPh @S (8)
2
2
A
mixture of
3
K[(SPMe )(SPPh )N] (0.33 g, 0.91 mmol) in 25 ml anhy-
(0.27 g, 0.92 mmol) and
2
2
drous CH Cl was stirred at room temperature for 12 h.
2
2
Then the KBr was filtered off and the clear yellow solu-
tion was concentrated in vacuo until a yellow solid
deposited. The solid was separated by filtration and
recrystallized from CH Cl /n-hexane (1:5, v/v) to give
2
2
5. Supplementary material
yellow crystals of 8. Yield: 0.27 g (55%). M.p. 108–
1
for C H N P S Se: C, 51.39; H, 5.25; N, 5.21%. H
10 ꢁC. Anal. Found: C, 51.03; H, 4.98; N, 5.11. Calc.
1
Crystallographic data for the structural analysis of
compounds 2, 4–8 have been deposited with the Cam-
bridge Crystallographic Data Centre CCDC Nos.
250623 (2), 250622 (4), 250773 (5), 250772 (6), 250621
2
3
28
2 2 2
2
NMR: d 1.99 d (6H, P–CH , J 13.1 Hz), 2.33s (6H,
3
PH
3
N–CH ), 3.67s (2H, –CH –), 7.08dd (1H, H , JHH
3
2
3
4
.3, JHH 1.1 Hz), 7.13ddd (1H, H ,
3
7
J
3
7.3,
7.6,
4
HH
3
4
JHH 7.3, J
(
7) and 250771 (8). Copies of the information may be
1.1 Hz), 7.22ddd (1H, H , J
5 HH
HH
3
4
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44
1223 336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
JHH 7.6, JHH 1.6 Hz), 7.29m (6H, P–C H -meta +
6
5
3
para), 7.95dm (4H, P–C H -ortho,
6
J
13.6 Hz),
0.8 Hz). C NMR: d
5
PH
13
3
.02dd (1H, H , J
4
8.0, J
8
2
6
HH
1
HH
3
1.42dd (P–CH3, JPC 71.1, JPC 3.2 Hz), 43.94 (N–
CH ), 63.73 (–CH –), 126.16 (C ), 126.91 (C ), 127.60d
3
3
2
4
3
(
(
C H -meta, JPC 12.9 Hz), 128.37 (C5), 129.58d
6 5
4
C H -para, J 2.7 Hz), 129.88 (C ), 130.67d (C H -
Acknowledgements
6
5
PC
6
6
5
2
ortho, JPC 11.2 Hz), 135.18 (C ), 137.97 (C ),
1
41.34dd (C H -ipso, JPC 107.4,
1
3
2
31
This work was supported by the National University
Research Council of Romania (CNCSIS Grants: AT-45/
1
J 6.1 Hz).
PC
P
6
5
3
1
NMR: d 40.8d (Me P-S, JPP 8.3, JPC 71.1 Hz ),
2.6d (Ph P@S, J 8.3, J
2
2003 and TD-96/2004). J.E.D. thanks the University of
3
1
77
4
107.7 Hz). Se NMR
PC
2
PP
Windsor and C.L.B.M., the Natural Sciences and Engi-
neering Research Council of Canada for financial
support.
(
CDCl ): d 579.9.
3
4
.9. X-ray structure determination
Block crystals of [(2-Me NCH )C H ]SeCl (2)
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