N→As intramolecularly coordinated organoarsenic(III) chalcogenides: Isolation of terminal As-S and As-Se bonds

Article abstract of DOI:10.1016/j.jorganchem.2012.10.029

Unprecedented NCN - intramolecularly chelated organoarsenic(III) sulfide and selenide LAsE (where L = [2,6-(Me₂NCH₂) ₂C₆H₃]^- and E = S (2) or Se (3)) were prepared by the reaction of the pa

Full text of DOI:10.1016/j.jorganchem.2012.10.029

Journal of Organometallic Chemistry 723 (2013) 10e14
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Journal of Organometallic Chemistry
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Communication
N/As intramolecularly coordinated organoarsenic(III) chalcogenides: Isolation
of terminal AseS and AseSe bonds
a
a
a
b
c
a,
*
ꢀ ꢁꢀ ꢀ
ꢀ
Jan Vrána , Roman Jambor , Ales Ruzicka , Antonín Lycka , Frank De Proft , Libor Dostál
a Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ-532 10 Pardubice, Czech Republic
b Research Institute for Organic Syntheses, Rybitví 296, CZ-533 54 Pardubice, Czech Republic
c Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, B-1050 Brussels, Belgium
a r t i c l e i n f o
a b s t r a c t
Article history:
Unprecedented NCN e intramolecularly chelated organoarsenic(III) sulfide and selenide LAsE (where
L ¼ [2,6-(Me2NCH2)2C6H3]ꢀ and E ¼ S (2) or Se (3)) were prepared by the reaction of the parent chloride
LAsCl2 (1) with Li2E. Analogously, the reaction of NC chelated compound L0AsCl2 (4) (where L0 ¼ [2-(20,60-
i-Pr2C6H3)N]CH)C6H4]ꢀ) with Li2S gave the corresponding sulfide L0AsS (5). The molecular structures of
3 and 4 were established in the solid state using X-ray diffraction technique.
Received 15 June 2012
Received in revised form
7 September 2012
Accepted 16 October 2012
Ó 2012 Elsevier B.V. All rights reserved.
Keywords:
Arsenic
Chalcogenides
Chelating ligands
Terminal bond
X-ray structures
1. Introduction
first terminal Sb]E (E ¼ S, Se, Te) bonds (Fig. 1A) [6]. In comparison
to the rich chemistry of organoantimony(III) and organo-
Significant progress has been recently achieved in the field of
preparation and structure description of heavier group 15 elements
(especially Sb(III), Bi(III)) organometallic chalcogenides, which
often show pronounced tendency to oligomerization [1]. Thus,
instead of stabilization of terminal RM]E bonds (where M ¼ Sb or
Bi; E ¼ S, Se, Te) dimers (RME)2, trimers (RME)3 or even higher
oligomers are formed with chalcogen atoms forming bridges
between the pnictogen atoms [1]. These compounds may be
stabilized either kinetically using bulky substituents or thermo-
dynamically by the presence of multidentate ligands and intra-
molecular N/M dative interaction. The bulky substituents were
successfully used by Tokitoh [2] and Breunig [3] et al. for stabili-
zation of series of both antimony and bismuth (poly)sulfides,
selenides and rare examples of tellurides including unprecedented
three-membered M2Te ring systems [4]. Nevertheless, compounds
with terminal M]E bonds could not be prepared as stable species
using this type of ligands. On the contrary, we and others have
demonstrated that using of NC- or NCN-chelating ligand represents
an interesting alternative for stabilization of these chalcogenides
[5] and using of NCN pincer type ligands allowed isolation of the
bismuth(III) chalcogenides corresponding organoarsenic(III)
compounds have gained only limited interest, among published
results the five-membered cycles RAs(E)(E2)AsR (E ¼ S, Se) [7] and
the only arsenic telluride derived from the 9,10-epichalcogeno-
9,10-dihydroarsathrene backbone (Fig. 1B) are noteworthy [8].
Organoarsenic(III) compounds with terminal As]E bonds are, to
the best of our knowledge, unknown and compound with simple
alkyl substituents tend to oligomerize [9]. As we were able to
observe terminal Sb]E bonds in compounds using advantage of
intramolecular interactions mediated by the NCN pincer type
ligands, we were interested whether the same or related NC
chelating ligand system will be good candidate for the stabilization
of the terminal As]E bonds.
Herein, we report the syntheses and structures of organo-
arsenic(III) chalcogenides LAsE (where L ¼ [2,6-(Me2NCH2)2C6H3]ꢀ
and E ¼ S (2) or Se (3)) and L0AsS (5) (where L0 ¼ [2-((20,60-i-
Pr2C6H3)N]CH)C6H4]ꢀ) containing terminal As]E bond (E ¼ S or
Se) both in the solid state and in solution.
2. Result and discussion
The intramolecularly coordinated organoarsenic(III) chloride
* Corresponding author.
E-mail address: libor.dostal@upce.cz (L. Dostál).
LAsCl2 (1) [10] reacts smoothly with in situ [11] prepared Li2S or
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.10.029

J. Vrána et al. / Journal of Organometallic Chemistry 723 (2013) 10e14
11
Fig. 1. (A) Compounds with terminal Sb]E bonds. (B) Structures of selected organoarsenic(III) chalcogenides.
Li2Se to yield expected molecular chalcogenides LAsE (where E ¼ S
(2) or Se (3), Scheme 1). Both compounds were isolated after
workup as colorless (2) or yellow (3) crystalline solids, which are
indefinitely stable under inert conditions. The identity of both
compounds was established by the help of elemental analysis and
1H and 13C NMR spectroscopy.
monomeric in solution as proved by the help of 1H and 13C NMR
spectra. Thus, the 1H NMR spectrum of both 2 and 3 revealed only
one set of signals, where the signal for the diastereotopic CH2N
protons are observed as an AX-type pattern at dA 2.87 and dx 3.77 for
2 (dA 2.86 and dx 3.80 for 3) and one singlet for N(CH3)2 protons. This
finding indicates both non-symmetric coordination environment of
the arsenic atom and the presence of rigid intramolecular N/As
interactions, which render rotation around the C(ligand)eAs bond
and, thus, proving the same monomeric structure as determined for
3 in the solid state. Similarly, the monomeric antimony chalcogen-
ides LSbE (E ¼ Se, Te) showed an AX-type pattern for the diaster-
eotopic CH2N protons, that was also ascribed to the rigid N/Sb
interactions and presence of terminal SbeE bonds. The 77Se NMR
The molecular structure of 3 was unambiguously determined by
the help of single crystal X-ray diffraction analysis [12] and is
depicted with relevant structural parameters in Fig. 2. The results of
the analysis proved an exclusively monomeric structure of 3 with
isolated terminal AseSe bond, which is the first example of such
ꢁ
a compound. The bond length As(1)eSe(1) 2.2736(5) A is signifi-
cantly shorter (6%) than the corresponding sum of the respective
ꢁ
covalent radii for the AseSe single bond Scov(As, Se) ¼ 2.37 A [13].
spectrum of 3 showed one signal at
the higher frequency in comparison with the analogous antimony
selenide LSbSe (
d 0.0 and this value is shifted to
This value also approaches the theoretically determined value of
ꢁ
2.21 A for the As]Se double bond by Pyykkö [13]. These facts
d
ꢀ153.0) [6a]. Another proof for the presence of
indicate multiple character of this bond, but the shortening of the
bond length may also be in part ascribed to the electrostatic
interaction between bonding partners, because the terminal bond
terminal AseS(Se) bonds stems from the Raman spectra, where only
one strong band at 453 cmꢀ1 for AseS bond in 2 and at 310 cmꢀ1 for
AseSe bond in 3 was observed. Both values are significantly shifted
is most probably polarized (As(
d
þ)eSe(
d-)) as recently proved by us
in closely related NCN chelated systems containing SbeE terminal
bonds (E ¼ S, Se, Te) [6]. The presence of partial positive charge on
the central arsenic atom is also reflected in the presence of two
strong intramolecular N/As interactions, where the bond lengths
As(1)eN(1) 2.312(3) and As(1)eN(2) 2.351(3) A are fairly shorter
than the sum of van der Waals radii SvdW(As, N) ¼ 3.75 A. The
ꢁ
ꢁ
coordination polyhedron of the central arsenic atom may be
described as a pseudo-trigonal bipyramid (so called see-saw
structure) with the nitrogen atoms located in the axial positions
(the bonding angle N(1)eAs(1)eN(2) 153.42(10)ꢁ) and the ipso-
carbon atom C(1), selenium atom Se(1) and the lone pair of elec-
trons occupy the equatorial positions. The value of the bonding
angle C(1)eAs(1)eSe(1) 100.99(9)ꢁ is more acute than ideal value
120ꢁ reflecting repulsion with the lone pair of arsenic.
The monomeric structure of 3 determined in the solid state is
retained in solution (C6D6) and, similarly, compound
2 is
Fig. 2. ORTEP view of 3. The thermal ellipsoids are drawn with 50% probabiliꢁty.
ꢁ
Benzene molecule is omitted for clarity. Selected bond distances (A) and angles ( ):
As(1)eC(1) 1.945(3), As(1)eSe(1) 2.2736(5), As(1)eN(1) 2.312(3), As(1)eN(2) 2.351(3),
N(1)eAs(1)eN(2) 153.42(10), C(1)eAs(1)eSe(1) 100.99(9), C(1)eAs(1)eN(1) 79.08(10),
C(1)eAs(1)eN(2) 78.27(10).
Scheme 1. Synthesis of the intramolecularly coordinated organoarsenic(III) chalco-
genides 2 and 3.

12
J. Vrána et al. / Journal of Organometallic Chemistry 723 (2013) 10e14
in comparison with the values usually obtained for the bridging Ase
S(Se)eAs bonds in oligo- or polymeric species [14].
To get some additional insight into the structures of compounds
2 and 3 and to describe the terminal As]E bonds in particular, DFT
calculations on these structures were performed using the
Gaussian 09 program [15]. Starting from the crystal structure of 3,
a geometry optimization of this molecule was performed at the
B3LYP [16]/cc-pVTZ [17] level of theory. The equilibrium geometry
obtained was found to be in good agreement with the crystal
structure of 3. In addition, the geometry of compound 2 was
optimized at the same level of theory. In order to probe the features
of the terminal AseS and AseSe bonds, an NBO analysis [18] was
performed on the optimized structures; in addition, the Wiberg
bond order [19] for these bonds were computed. From this analysis,
it can be stated that, as was previously found for organo-
antimony(III) compounds containing antimonyeselenium and e
tellurium terminal bonds [6a], the bond between As and S or Se
is intermediate between a polarized single bond and a double bond.
The NBO charge on As amounts to þ0.830 and þ0.740 in 2 and 3
respectively, the charge on S and Se being ꢀ0.726 and ꢀ0.645,
respectively. For compound 2, the Wiberg bond order for the AseS
bond order is 1.481, whereas in the case of the AseSe bond it is
1.475. For comparison, the corresponding values in the compounds
LSbSe and LSbTe are 1.409 and 1.426, respectively [6a].
The ligand L0 has been investigated to test the possible stabili-
zation of similar monomeric arsenic(III) chalcogenides by only one
N-donor functionality (Scheme 2). The starting chloride L0AsCl2 (4)
was prepared by conversion of the lithium precursor with arsen-
ic(III) chloride in diethylether. Compound 4, stable under inert
conditions, was isolated as yellowish crystals in high yield. The
identity of 4 was established by the help of elemental analysis and
1H and 13C NMR spectroscopy. The molecular structure of 4 was
proven by the help of single crystal X-ray diffraction analysis [12]
and is depicted with relevant structural parameters in Fig. 3. The
nitrogen donor atom of L0 ligand is strongly coordinated to the
central arsenic atom with the As(1)eN(1) bond length of
Fig. 3. ORTEP view of 4. The thermal ellipsoids are drawn with 50% probabiliꢁty.
ꢁ
Hydrogen atoms are omitted for clarity. Selected bond distances (A) and angles ( ):
As(1)eC(1) 1.959(4), As(1)eCl(1) 2.3299(10), As(1)eCl(2) 2.2043(9), As(1)eN(1)
2.329(3), N(1)As(1)eCl(1) 171.94(8), C(1)eAs(1)eCl(1) 95.46(9), C(1)eAs(1)eCl(2)
97.48(9), C(1)eAs(1)eN(1) 77.94(12).
suitable single crystals for X-ray diffraction analysis failed and, thus,
we are not able to speculate about the structure in the solid state.
Nevertheless, the 1H and 13C NMR spectra of 5 revealed only one set
of signals for the ligand L0 (see Experimental). Furthermore, upon
cooling the sample of 5 in C7D8 to 200 K the signals of the i-Pr
groups on the flanking aromatic rings became non-equivalent
suggesting the non-symmetric environment around the central
arsenic atom. The Raman spectrum of 5 revealed four medium to
strong bands at 331, 339, 364 and 375 cmꢀ1, which are significantly
shifted in comparison with value found for the terminal AseS bond
in 2 (453 cmꢀ1). More importantly, these values fall within the
interval typical for bridging AseSeAs groups [14]. These facts
indicate oligomeric structure of 5 formed via AseSeAs bridges.
ꢁ
2.329(3) A. This value is comparable with the N/As interaction
ꢁ
(2.351(9) A) observed in the related N,C chelated compound
[8-(Me2N)C10H6]AsCl2 [20]. The coordination polyhedron of the
central atom may be described as a see-saw structure, similarly to 3,
with the N(1) and Cl(1) atom occupying the axial position (the
bonding angle N(1)As(1)eCl(1) is 171.94(8)ꢁ) and the equatorial
plane is formed by the ipso-C(1) atom, the chlorine atom Cl(2) and
the lone pair of the arsenic atom.
The reactions of 4 with lithium chalcogenides Li2E (E ¼ S, Se)
were studied. In the case of the selenide, only a complicated
mixture of non-separable products was observed, however the
reaction of 4 with Li2S gave smoothly the expected sulfide L0AsS
(Scheme 2) as a bright yellow air sensitive solid. The identity of 5
was established by the help of elemental analysis and 1H and 13C
NMR spectroscopy. Unfortunately, all numerous attempts to obtain
3. Conclusion
In conclusion, we have demonstrated that NCN chelating ligand
L is a good candidate for preparation of molecular organoarsenic(III)
sulfide and selenide. The application of the ligand L allowed
Scheme 2. Synthesis of the intramolecularly coordinated organoarsenic(III) compounds 4 and 5.

J. Vrána et al. / Journal of Organometallic Chemistry 723 (2013) 10e14
13
successful isolation of unprecedented compounds with preserved
terminal AseS(Se) bonds both in the solid state and in solution. It is
worth mentioning that development and utilization of more robust
chelating ligands will be necessary for preparation of corresponding
tellurides. Only the organoarsenic(III) sulfide could be prepared
using the ligand L0 proving significantly lower potential for stabili-
zation of arsenic chalcogenides in the case of L0, furthermore this
ligand is not able to stabilize terminal AseS bond.
((CH3)2N), 62.0 (CH2N), 124.8 (AreC3,5), 128.4 (AreC4), 141.0 (Are
C2,6), 152.7 (AreC1). Raman (cmꢀ1): 310 (vs) AseSe.
4.4. Synthesis of compound 4
A solution of n-BuLi (2.2 mL, 3.43 mmol, 1.6 M solution in
hexane) was added to a solution of 2-((20,60-i-Pr2C6H3)N]CH)
C6H4Br (1.18 g, 3.43 mmol) in diethylether (50 mL) at ꢀ70 ꢁC and
stirred for 1 h at this temperature. The resulting yelloweorange
suspension of the lithium compound was added to a solution of
AsCl3 (0.29 mL, 3.43 mmol) in diethylether (30 mL) pre-cooled
to ꢀ78 ꢁC. The resulting mixture was allowed to reach room
temperature and stirred for additional 90 min. The yellowish
precipitate was filtered and washed with additional hexane
(10 mL). The precipitate was extracted with benzene (50 mL) and
the obtained yellow extract was evaporated to dryness and washed
with hexane (10 mL) to give 4 as yellowish powder. The single
crystals were obtained by recrystallization from benzene/hexane
mixture. Yield: 1.19 g (85%). Mp. 169e171 ꢁC. Anal. calcd for
4. Experimental
4.1. General methods
The starting compounds [2,6-(Me2NCH2)2C6H3]AsCl2 [10], and
2-((20,60-i-Pr2C6H3)N]CH)C6H4Br [21] were prepared according to
the literature procedures. The THF solutions of Li2S and Li2Se were
prepared from sulfur (selenium) and Li[B(Et)3H] according to the
literature procedure and used in situ [11]. All solvents were dried by
standard procedures. The 1H, 13C, 77Se NMR spectra were recorded
on a Bruker Avance500 at 300 K in C6D6 at 500.13, 125.77 and
C
19H22AsCl2N (410.21 g molꢀ1): C, 55.6; H, 5.4. Found: C, 55.8; H,
5.7. 1H NMR (C6D6, 500 MHz):
1.02 (d (br), 12H, CH(CH3)2), 2.86
95.38 MHz, respectively. The 1H, 13C, NMR chemical shifts
d are
d
(sept, 2H, CH(CH3)2), 6.86 (d, 1H, C6H4), 6.94 (d, 1H, C6H4), 7.10 (m,
given in ppm and referenced to the residual signals of the solvent
4H, 20,60-i-Pr2C6H3 and C6H4), 7.45 (s, 1H, CH]N), 8.97 (dd, 1H,
(C6D6:
d
(1H) ¼ 7.16 ppm,
d
(
13C) ¼ 128.39 ppm). The 77Se chemical
C6H4). 13C NMR (C6D6, 125.77 MHz):
d 24.2 (s, CH(CH3)2), 25.2 (s,
shifts were determined using
proton frequency 100.00 MHz (i.e.,
X
¼ 19.071513 MHz corresponding to
77Se) ¼ 0.0 at 95.382358 MHz
CH(CH3)2), 29.1 (s, CH(CH3)2), 124.5, 127.5, 131.8, 132.0, 133.4, 134.4,
137.5, 140.5, 143.4, 148.4 (s, AreC), 165.4 (s, CH]N).
d(
for proton frequency 500.13 MHz). Elemental analyses were per-
formed on an LECO-CHNS-932 analyzer. Raman spectra of samples
sealed in quarts capillaries were recorded on a Bruker IFS 55 with
4.5. Synthesis of compound 5
FRA 106 extension in region 50e3500 cmꢀ1
.
A solution of Li2S (0.89 mmol, prepared from 29 mg of sulfur,
and 1.8 mL of 1 M THF solution of Li[B(Et)3H]) in THF (20 mL) was
added to a solution of L0AsCl2 (318 mg, 0.78 mmol) in 30 mL of THF.
Upon addition, the white material precipitated and the resulting
mixture was stirred for additional 1 h at r.t. The reaction mixture
was evaporated to dryness, and extracted with toluene (30 mL). The
yellow extract was evaporated to ca. 10 mL and hexane (15 mL) was
added resulting to precipitation of yellowish material (from the
mother liquor second crop was obtained by next addition of hexane
and storage at 5 ꢁC), which was filtered and washed with hexane
(2 ꢂ 5 mL) to give yellowish solid characterized as 5. The product
was may be recrystallized from toluene. Yield: 244 mg (85%). Mp.
215e217 ꢁC. Anal. calcd for C19H22AsNS (371.37 g molꢀ1): C, 61.5; H,
4.2. Synthesis of compound 2
A solution of Li2S (2.61 mmol, prepared from 84 mg of sulfur,
and 5.2 mL of 1 M THF solution of Li[B(Et)3H]) in THF (20 mL) was
added to a solution of LAsCl2 (761 mg, 2.27 mmol) in 30 mL of
CH2Cl2. Upon addition, the browneorange material precipitated
and the resulting mixture was stirred for additional 1 h at r.t. The
reaction mixture was evaporated to dryness, and extracted with
toluene (30 mL). The yellow extract was evaporated and the
resulting material was washed with hexane (2 ꢂ 10 mL) to give
yellowish solid characterized as 2. Yield: 420 mg (62%). Mp. 102e
104 ꢁC. Anal. calcd for C12H19AsN2S (298.28 g molꢀ1): C, 48.3; H,
6.0. Found: C, 61.3; H, 5.8. 1H NMR (C6D6, 500 MHz):
d 1.13 (d (br),
6.4. Found: C, 48.5; H, 6.5. 1H NMR (C6D6, 500 MHz):
12H, (CH3)2N), 2.87 and 3.77 (AX system, 4H, CH2N), 6.76 (d, 2H,
AreH3,5), 7.04 (t, 1H, AreH4). 13C NMR (C6D6, 125.77 MHz):
44.9
((CH3)2N), 62.1 (CH2N), 124.9 (AreC3,5), 128.7 (AreC4), 141.4 (Are
C2,6), 153.4 (AreC1). Raman (cmꢀ1): 453 (s) AseS.
d 2.21 (s (br),
12H, CH(CH3)2), 3.26 (sept, 2H, CH(CH3)2), 7.00 (m, 6H, 20,60-i-
Pr2C6H3 and C6H4), 8.03 (s, 1H, CH]N), 8.32 (dd, 1H, C6H4). 13C NMR
d
(C6D6, 125.77 MHz): d 24.2 (s, CH(CH3)2), 25.2 (s, CH(CH3)2), 28.9 (s,
CH(CH3)2), 124.1, 126.0, 129.9, 131.3, 133.6, 135.7, 137.5, 139.5, 144.9,
147.4 (s, AreC), 164.7 (s, CH]N). 1H NMR (C7D8, 500 MHz, 200 K):
d
0.96, 1.04, 1.11 and 1.27 (four doublets, 12H, CH(CH3)2), 3.24 (sept
4.3. Synthesis of compound 3
(br), 2H, CH(CH3)2), 6.77 (d, 1H, C6H4), 6.93 (d, 1H, C6H4), 7.05 (m,
4H, 20,60-i-Pr2C6H3 and C6H4), 7.80 (s, 1H, CH]N), 8.36 (d, 1H, C6H4).
Raman (cmꢀ1): 331(s), 339(s), 364(m), 375(s) SeAseS.
A solution of Li2Se (3.63 mmol, prepared from 287 mg of sele-
nium powder, and 7.3 mL of 1 M THF solution of Li[B(Et)3H]) in THF
(30 mL) was added to a solution of LAsCl2 (1.09 g, 3.16 mmol) in
30 mL of CH2Cl2. Upon addition, the brownered material precipi-
tated and the resulting mixture was stirred for additional 1 h at r.t.
The reaction mixture was evaporated to dryness, and extracted
with toluene (50 mL). The bright yellow extract was evaporated to
ca. 10 mL and storage of this solution at 5 ꢁC for overnight gave
yellow single crystals of 3, which were separated by decantation
and washed with hexane (10 mL). Yield: 501 mg (46%). Mp. 140 ꢁC.
Anal. calcd for C12H19AsN2Se (345.17 g molꢀ1): C, 41.8; H, 5.6.
4.6. X-ray structure determination
The suitable single crystal of 3 and 4 were mounted on glass
fiber with an oil and measured on four-circle diffractometer
KappaCCD with CCD area detector by monochromatized MoKa
ꢁ
radiation (
l
¼ 0.71073 A) at 150(1) K. The numerical [22] absorption
corrections from crystal shape were applied for all crystals. The
structures were solved by the direct method (SIR92) [23] and
refined by a full matrix least squares procedure based on F2
(SHELXL97) [24]. Hydrogen atoms were fixed into idealized posi-
tions (riding model) and assigned temperature factors Hiso
(H) ¼ 1.2 Ueq (pivot atom) or of 1.5 Ueq for the methyl moiety with
Found: C, 42.1; H, 5.8. 1H NMR (C6D6, 500 MHz):
(CH3)2N), 2.86 and 3.80 (AX system, 4H, CH2N), 6.78 (d, 2H, Are
H3,5), 7.04 (t, 1H, AreH4). 13C NMR (C6D6, 125.77 MHz):
45.2
d 2.13 (s (br), 12H,
d

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J. Vrána et al. / Journal of Organometallic Chemistry 723 (2013) 10e14
ꢁ
ꢁꢀ ꢀ
ꢀ
[6] (a) L. Dostál, R. Jambor, A. Ruzicka, A. Lycka, J. Brus, F. de Proft, Organome-
tallics 27 (2008) 6059;
CeH ¼ 0.96, 0.97, and 0.93 A for methyl, methylene, and hydrogen
atoms in aromatic ring, respectively.
ꢀ
ꢁꢀ ꢀ
ꢀ
(b) P. Simon, R. Jambor, A. Ruzicka, A. Lycka, F. De Proft, L. Dostál, Dalton Trans.
(2012) 5140;
ꢀ
ꢁꢀ ꢀ
ꢀ
ꢀ
(c) L. Dostál, R. Jambor, A. Ruzicka, R. Jirásko, E. Cernosková, L. Benes, F. de
Proft, Organometallics 29 (2010) 4486.
Acknowledgments
[7] (a) T. Zell, W. Shi, R. Langer, L. Ponikiewski, A. Rothenberger, Dalton Trans.
(2008) 932;
The authors wish to thank the Grant Agency of the Czech
Republic (project no. P207/10/0130). FDP wishes to acknowledge
the Research Foundation Flanders (FWO) and the Free University of
Brussels (VUB).
(b) A. Terzis, V.I. Ioannou, Z. Anorg. Allg. Chem. 630 (2004) 278;
(c) C.A. Applegate, E.A. Meyers, R.A. Zingaro, A. Merijanian, Phosphorus, Sulfur
Silicon Relat. Elem. 35 (1988) 363.
[8] D.W. Allen, J.C. Coppola, O. Kennard, F.G. Mann, W.D.S. Motherwell,
D.G. Watson, J. Chem. Soc. C Org. 6 (1970) 810.
[9] For example see: A.J. DiMaio, A.L. Rheingold Inorg. Chem. 29 (1990) 798.
[10] D.A. Atwood, A.H. Cowley, J. Ruiz, Inorg. Chim. Acta 198e200 (1992) 271.
[11] U. Herzog, G. Rheinwald, Organometallics 20 (2001) 5369.
[12] 3: C12H19AsN2Se$0.5(C6H6), monoclinic, P21/c, a ¼ 13.4939(5), b ¼ 8.7070(5),
Appendix A. Supplementary material
CCDC 835515 and 835513 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
126.739(3)ꢁ,
V
¼
1597.52(13) A ,
Z
¼
4, R1 (obs.
3
ꢁ
c
¼
16.9671(4),
b
¼
data) ¼ 0.032, wR2 (all data) ¼ 0.062. CCDC 876703. 4: C19H22AsCl2N, triclinic,
P21/c, a ¼ 9.6430(6), b ¼ 13.4721(9), c ¼ 16.7960(10),
b
¼ 120.109(5)ꢁ,
3
ꢁ
V ¼ 1887.6(2) A , Z ¼ 4, R1 (obs. data) ¼ 0.047, wR2 (all data) ¼ 0.068. CCDC
876704.
[13] (a) P. Pyykkö, M. Atsumi, Chem. Eur. J. 15 (2009) 186;
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Appendix B. Supplementary material
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2012.10.029.
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