Compounds of the types Pn(pyS)3(Pn = P, As, Bi; PyS: Pyridine-2-thiolate) and Sb(pyS)xPh3-x(x = 3-1); Molecular structures and electronic situations of the Pn atoms

Article abstract of DOI:10.1515/znb-2020-0171

The compounds Pn(pyS)3 (Pn = P, As, Sb, Bi) were synthesized from the respective chloride (Pn = P, As, Sb) or nitrate (Bi), pyridine-2-thiol (pySH) and triethylamine (NEt3) as a supporting base in THF (P, Sb), CHCl3 (As) or methanol (Bi). Sb(pyS)3 was also obtained from the reaction of SbCl3 with LipyS (prepared in situ) in methanol. The compounds Sb(pyS)2Ph and Sb(pyS)Ph2 were prepared in a one-pot reaction starting from SbCl3 and SbPh3 (1:1 ratio). Upon Cl/pyS substitution, the resulting reaction mixture allows for a facile separation of the products in hot hexane. P(pyS)3 and As(pyS)3 crystallize isostructurally to the reported structure of Sb(pyS)3 with κ-S-bound pyS ligands. These crystal structures feature close Pn···Pn contacts which are most pronounced for the arsenic derivative. Bi(pyS)3 adopts a different molecular structure in the solid state, which features two chelating (κ2-S,N-pyS) ligands and a κ-S-bound ligand. The presence of N→Bi interactions between the nitrogen atom of the κ-S-pyS ligand and the Bi atom of another molecule renders this structure a polymer chain along the crystallographic b axis with BiBi van-der-Waals contacts. The structures of this set of Pn(pyS)3 compounds were also studied in solution using 1H NMR spectroscopy, revealing equivalent pyS ligands in discrete Pn(pyS)3 molecules. The molecular structure of Sb(pyS)Ph2 was optimized by quantum chemical methods, and a comparison with the structures reported for the other Sb/pyS/Ph combinations reveals Sb(pyS)2Ph to feature the strongest Sb···N interactions with the κ-S-pyS ligand. The results of 1H NMR spectroscopic investigations of the compounds Sb(pyS)xPh3-x (x = 3-0) suggest the Ph protons in ortho position to be incorporated into intramolecular C-H···S contacts for x = 2 and 1. Natural localized molecular orbital (NLMO) calculations were employed in order to gain insights into the electronic situations of the Pn atoms and Pn-R bonds (R = S, C), especially for the effects caused by formal substitution of Pn in the compounds Pn(pyS)3 and the ligand patterns in the compounds Sb(pyS)xPh3-x (x = 3-0). For the latter series of compounds, the electronic situation of the Sb atom was further studied by 121Sb M?ssbauer spectroscopy, providing a correlation between the calculated electron density at Sb [ρ(0)] and the experimentally observed isomer shift δ. The missing link between group 15 and group 13 metal compounds of the type M(pyS)3, compound Al(pyS)3, was synthesized in this work. In the solid state (confirmed crystallographically), the mer isomer of this tris-chelate complex with distorted octahedral Al coordination sphere was found. This coordination mode was confirmed for the solution state (CDCl3) by 1H and 13C NMR spectroscopy at T = -40 °C.

Full text of DOI:10.1515/znb-2020-0171

Z. Naturforsch. 2021; 76(2)b: 103–118
Erik Wächtler, Robert Gericke, Theresa Block, Birgit Gerke, Rainer Pöttgen and Jörg Wagler*
Compounds of the types Pn(pyS) (Pn = P, As, Bi;
3
pyS: pyridine-2-thiolate) and Sb(pyS) Ph
x 3–x
(
x = 3–1); molecular structures and electronic
situations of the Pn atoms
https://doi.org/10.1515/znb-2020-0171
was optimized by quantum chemical methods, and a
Received October 14, 2020; accepted December 12, 2020;
published online January 15, 2021
comparison with the structures reported for the other Sb/
pyS/Ph combinations reveals Sb(pyS) Ph to feature the
2
strongest Sb···N interactions with the κ-S-pyS ligand. The
results of H NMR spectroscopic investigations of the
Abstract: The compounds Pn(pyS) (Pn = P, As, Sb, Bi)
3
1
were synthesized from the respective chloride (Pn = P, As,
Sb) or nitrate (Bi), pyridine-2-thiol (pySH) and triethyl-
amine (NEt ) as a supporting base in THF (P, Sb), CHCl (As)
compounds Sb(pyS) Ph (x = 3–0) suggest the Ph protons
x
3–x
in ortho position to be incorporated into intramolecular C–
H···S contacts for x = 2 and 1. Natural localized molecular
orbital (NLMO) calculations were employed in order to gain
insights into the electronic situations of the Pn atoms and
Pn–R bonds (R = S, C), especially for the effects caused by
3
3
or methanol (Bi). Sb(pyS) was also obtained from the re-
3
action of SbCl with LipyS (prepared in situ) in methanol.
3
The compounds Sb(pyS) Ph and Sb(pyS)Ph were prepared
2
2
in a one-pot reaction starting from SbCl and SbPh (1:1
3
3
formal substitution of Pn in the compounds Pn(pyS) and
3
ratio). Upon Cl/pyS substitution, the resulting reaction
mixture allows for a facile separation of the products in hot
hexane. P(pyS) and As(pyS) crystallize isostructurally to
the ligand patterns in the compounds Sb(pyS) Ph
x
3–x
(
x = 3–0). For the latter series of compounds, the electronic
3
3
121
situation of the Sb atom was further studied by Sb
Mössbauer spectroscopy, providing a correlation between
the calculated electron density at Sb [ρ(0)] and the exper-
imentally observed isomer shift δ. The missing link be-
tween group 15 and group 13 metal compounds of the type
M(pyS) , compound Al(pyS) , was synthesized in this
the reported structure of Sb(pyS) with κ-S-bound pyS li-
3
gands. These crystal structures feature close Pn···Pn con-
tacts which are most pronounced for the arsenic derivative.
Bi(pyS) adopts a different molecular structure in the solid
3
2
state, which features two chelating (κ -S,N-pyS) ligands
3
3
and a κ-S-bound ligand. The presence of N→Bi interactions
between the nitrogen atom of the κ-S-pyS ligand and the Bi
atom of another molecule renders this structure a polymer
chain along the crystallographic b axis with Bi⋅⋅⋅Bi van-der-
Waals contacts. The structures of this set of Pn(pyS)3
work. In the solid state (confirmed crystallographically),
the mer isomer of this tris-chelate complex with distorted
octahedral Al coordination sphere was found. This coor-
dination mode was confirmed for the solution state (CDCl )
3
1
13
by H and C NMR spectroscopy at T = −40 °C.
1
compounds were also studied in solution using H NMR
spectroscopy, revealing equivalent pyS ligands in discrete Keywords:
Mössbauer spectroscopy;
pnictogens;
Pn(pyS) molecules. The molecular structure of Sb(pyS)Ph2 pyridine-2-thiolate; quantum chemical calculations; X-ray
3
diffraction.
*
Corresponding author: Jörg Wagler, Institut für Anorganische
Dedicated to: In memory of Professor Edwin Weber who was a great
teacher of organic chemistry.
Chemie, Technische Universität Bergakademie Freiberg, Leipziger
Straße 29, 09596 Freiberg, Germany,
E-mail: joerg.wagler@chemie.tu-freiberg.de
Erik Wächtler, Institut für Anorganische Chemie, Technische
Universität Bergakademie Freiberg, Leipziger Straße 29, 09596
Freiberg, Germany
1
Introduction
Robert Gericke, Institut für Anorganische Chemie, Technische
Universität Bergakademie Freiberg, Leipziger Straße 29, 09596
Freiberg, Germany; and School of Chemistry, Trinity College Dublin,
The combination of hard (N) and soft (S) donor atoms as
well as the bent N–C–S motif enables the pyridine-
−
2
-thiolate anion (pyS ) to adopt a variety of coordination
152–160 Pearse Street, Dublin 2, Ireland
modes both in transition metal (TM) and main group metal
Theresa Block, Birgit Gerke and Rainer Pöttgen, Institut für
Anorganische und Analytische Chemie, Universität Münster,
Corrensstraße 30, 48149 Münster, Germany
2
or metalloid (M) chemistry, e.g. chelating (κ -S,N), bridging
(µ-S,N or µ-S), or monodentate (κ-S, κ-N). Several Pd and Pt

1
04
E. Wächtler et al.: Main group coordination chemistry
complexes featuring the pyS ligand were synthesized the structure of Sn(pyS) ·pySH [16], we have recently pre-
4
2
which show κ -S,N versus κ-S ligand scrambling of two pyS sented the structures of the homoleptic compounds
ligands [1], or adopt dinuclear paddle wheel-shaped M (pyS) (V, M = Si, Sn; two chelating, two κ-S-bound
1
4
14
4
structures [2]. Unusual eightfold coordination was reported pyS ligands) and Sn(pyS) (VI, with dimeric and polymeric
2
4
for the mononuclear homoleptic complexes TM (pyS)
(
structures in the solid state) [17]. The investigations on the
TM = Ti, Zr) [3]. In general, the coordination chemistry of coordination chemistry of the pyS anion in the coordina-
4
4
–
this ligand system in transition metal chemistry has tion sphere of Si by Tacke yielded complexes which are not
already been extensively studied [4]. homoleptic [18]. Lead(II) complexes have been structurally
In main group metal chemistry, the literature covers characterized for pyS ligands featuring –CF [19] or –SiMe3
3
some examples of X-ray diffraction studies of the structures [20] substituents in 3-position of the pyridine ring, how-
of homoleptic pyS compounds, or complexes featuring ever, the solid state structure of the parent complex
additional neutral ligands (for alkali and alkaline earth Pb(pyS) is unknown. In the last years, we became inter-
2
metals) for the completion of the coordination sphere. In ested in the compounds Sb(pyS) and Sb(pyS) Ph as we
3
2
this regard, the crown ether complexes of the Li, Na, and K have applied them as ligands for Rh [21] and Pt [22] com-
−
salts of pyS have been isolated and structurally charac- plexes. In these TM–Sb complexes, two pyS ligands bridge
2
terized, revealing chelating (κ -S,N) or unusual the TM–Sb core and, as a result of the charge delocalization
–
µ-S,N-bridging pyS coordination (Scheme 1, e.g. Na(pyS) within the anionic ligand, a variety of different coordina-
2
[
15-Crown-5], I) [5]. The κ -S,N mode was observed for the tion modes of Sb are accessible. In these cases, the question
Mg complexes Mg(pyS) (L) (II; L = THF, py) [6, 7], while the arose as to whether the TM–Sb bonds should be referred to
2
2
3
1
13
compounds of the type M (pyS) (III; M = In, Ga) feature as covalent or dative. Related studies focused on the
hexacoordinate metal centers with three κ -S,N chelating structures of similar TM–M (M = Ge, Sn) complexes
pyS ligands [8–10]. As other examples of pyS containing [23–27] or on a series of TM–Sb complexes [28, 29] with the
compounds, the Na and K salts of the borates oxygen analogue of pyS, i.e. 2-pyridyloxy in the µ-O,N
BH (pyS) [11] and BH(pyS)3 (IV) [12], respectively, should bridging mode.
3
2
14
14
–
1
3
M
−
−
2
2
be mentioned. Their anions feature monodentate κ-N co-
ordination toward the boron atom and, due to the dangling M (pyS) (M = pnictogen Pn = P, As, Sb, Bi) appears to be
Therefore a whole library of the compounds of the type
1
5
15
3
sulfur atom, they can further be applied in salt elimination available as starting materials for the syntheses of heter-
reactions for the synthesis of metal complexes via TM–S ometallic complexes. Except for the crystal and molecular
coordination [13–15]. Based upon the initial report on structures of Sb(pyS) (determined by single-crystal X-ray
3
Scheme 1: Compounds I–VI as examples of main group metal or metalloid compounds featuring the pyS ligand.

E. Wächtler et al.: Main group coordination chemistry
105
diffraction) [30, 31], and its derivative Sb(pyS) Ph [32], no
For the syntheses of Pn(pyS) (Pn = P, As, Sb), we have
3
2
reports on solid-state structures of the other homoleptic now employed the commercially available chlorides PnCl3
pnictogen derivatives have been published yet. For Pn = As using NEt as a supporting base. HNEt Cl salt elimination
3
3
[
33] and Bi [34, 35], procedures for their synthesis are proved to be a suitable method for Pn = P, As, Sb for re-
known (the As derivative was also studied in terms of its actions performed in THF (P, Sb; products good to mod-
reactivity [36–38]). However, detailed preparation methods erate solubility, hydrochloride poor solubility) or CHCl3
and comprehensive analytical data (e.g. NMR, single- (As, product poor solubility, hydrochloride good solubility;
crystal X-ray diffraction, calculations of electronic struc- As(pyS) recrystallized from boiling toluene). However, for
3
tures) are lacking. To the best of our knowledge, the com- Pn = Sb we noticed that occasionally at larger scale pro-
pound P(pyS) is still unknown. Therefore, we report herein cedures (several grams), the synthesis in THF via this route
3
on the synthesis and characterization of the full set of the causes problems with the separation of the pnictogen thi-
compounds Pn(pyS) (Pn = P, As, Sb, Bi). Special emphasis olate and HNEt Cl caused by their similar solubilities (see
3
3
is given on the comparison of the data for all complexes, i.e. below for the discussion of the trend in the solubilities and
the effect of the individual Pn atom on the structure and melting points of the compounds for Pn = P, As, Sb). Hence,
properties. We also include the series of compounds for the Sb compound we have further tested the reaction of
Sb(pyS) Ph (x = 3–0) into this survey in order to exhibit SbCl with the Li salt of pySH (prepared in situ) in meth-
x
3–x
3
the effect of a partial substitution of pyS substituents by anol, yielding Sb(pyS) in high yield and without LiCl
3
phenyl groups by introducing one example of a hetero- contamination.
leptic class of compounds. In this particular case of
For the preparation of Bi(pyS) , we used Bi(NO ) ·5H O
3 3 3 2
Pn = Sb, the feasibility of Mössbauer spectroscopy (of the and pySH as starting materials in methanol, in combina-
121
Sb nucleus) provides an excellent experimental probe for tion with NEt as a supporting base, according to the syn-
3
the state of bonding of the Pn atom, which can be corre- thesis of compound Bi(2-S-C H N-3-SiMe ) [31]. Bi(pyS)
3
5
3
3 3
lated with the results of quantum chemical (natural local- shows very poor solubility in common organic solvents
ized molecular orbital) calculations. The Ph substituent such as chloroform, dichloromethane, THF, diethyl ether
was chosen because Sb(pyS) Ph and SbPh had already and toluene, which hampered the facile synthesis of a
2
3
been reported and the latter also serves as a convenient crystalline product. The syntheses of the compounds
starting material for the synthesis of the two other hetero- Pn(pyS) (Pn = P, As, Sb, Bi), which resulted in good yields
3
leptic derivatives.
(above 70%), are summarized in Scheme 2.
The crystals of P(pyS) (obtained during synthesis) and
3
As(pyS) (recrystallization from boiling toluene) were sub-
3
2
Results and discussion
ject to X-ray structure determinations and were shown to
crystallize isostructurally to Sb(pyS) (trigonal space group
3
¯
2.1 Syntheses and structures
R3c, Table 1) [39]. Hence, differences in packing effects
Different approaches have been employed so far for the
synthesis of Pn(pyS) (Pn = As, Sb, Bi; no report on the
3
phosphorus compound): The arsenic derivative was re-
ported to form in the reaction of As O with pySH in
2
3
methanol (identity was confirmed just by elemental anal-
ysis) [33], whereas NEt was used as a supporting base in
3
the reaction of Sb(OAc) with pySH in the same solvent to
3
give Sb(pyS) (elemental and X-ray structure analysis) [31].
3
Bi(pyS) was synthesized either by oxidative addition of
3
dipyridyl disulfide to Bi metal (elemental analysis, IR
spectroscopy) [35] or by reactions of Bi(III) nitrate com-
1
pounds with pySH ( H NMR) [34]. However, we found that
both the experimental procedures and analytical data
(X-ray structure determination, NMR spectroscopy) could
be improved in terms of comprehensiveness and particu-
larly with respect to the comparison of all pnictogen de-
rivatives (regarding the specific effects of the Pn atoms).
3
Scheme 2: Syntheses of the compounds Pn(pyS) (Pn = P, As, Sb, Bi).

106
E. Wächtler et al.: Main group coordination chemistry
within the crystal structure can be neglected for the discus-
The solubility of the compound Bi(pyS) is very poor.
3
sion of the metrical parameters of these Pn(pyS) molecules Small amounts can be recrystallized e.g. from boiling iso-
3
(
(
Table 2). The Pn atoms are located on a special position butyl methyl ketone or by slow evaporation of a saturated
Wyckoff position 12c) and therefore, the asymmetric unit chloroform solution. The crystals obtained by these
consists of a third of a Pn(pyS) molecule. The molecular methods reveal a needle-shaped habitus and are split. The
3
structure of As(pyS) is depicted as an example in Figure 1 best crystal quality was obtained by slow evaporation (over
3
(left).ThepySligandsareκ-S-boundtothePncentralatomin a period of 10 days at room temperature) of a chloroform
a trigonal pyramidal fashion (S–Pn–S ca. 90°). The N atoms solution (15 mL) to which was added a small amount (2 mL)
point toward Pn, resulting in a [3+3] pseudo-octahedral co- of iso-butanol. However, the crystals were twinned, and the
ordinationandinsomewhatlongerPn–Sbondscomparedto data collection and their processing, and the structure so-
those in the corresponding pnictogen benzenethiolates lution and refinement were challenging (for details see
(
Pn(SPh) : Pn = P: 2.12 [40]; As: 2.24 [41]; Sb: 2.42 Å [42]; Supplementary Material available online). Nevertheless,
3
Pn(pyS) : Pn = P: 2.16; As: 2.28; Sb: 2.47 Å). Due to the the structure could be solved and refined reasonably well,
3
increasing atomic radii of Pn, the Pn–S bond lengths revealing Bi(pyS) to crystallize in the monoclinic space
3
increase in the order P < As < Sb, but the S–Pn–N angles group Cc with cell parameters close to the hexagonal
decrease (Pn = P: 62.3; As: 61.6; Sb: 59.3°). The Pn–N crystal system (Table 1).
distances are similar for all three compounds (P: 2.85; As:
The asymmetric unit consists of one Bi(pyS) molecule
3
2.82; Sb: 2.84 Å) which is a result of the interplay of two featuring two chelating and one κ-S-bound ligands. The N
effects: The atomic radii of Pn increase, leading to longer atom of the latter is coordinated to the Bi atom of another
2
bonds; with higher atomic number, the tendency of Pn to molecule, leading to a [Bi(κ -S,N-pyS) (μ-S,N-pyS)] poly-
2
n
adopt higher coordination numbers rises (stronger Pn–N mer chain (along the crystallographic b axis) with Bi⋅⋅⋅Bi
interactions). The order of the decreasing S–Pn–S angles van-der-Waals contacts and a total coordination number of
P (93.7°) > As (91.7°) > Sb (89.9°) is in accord with VSEPR the pnictogen atom of 6 (see Figure 2 for graphical repre-
theory as the electronegativity of Pn decreases in the same sentation and Table 2 for metrical parameters). The coor-
order and the Pn–S bond electron pairs are shifted toward dination geometry of the Bi atom can neither be described
the S atoms. The same observation was made for the as regular octahedral nor as trigonal prismatic. Three Bi–S
Pn(SPh ) compounds, even though the S–Pn–S angles in bonds are arranged trigonal pyramidally with S–Bi–S an-
3
3
thesecompoundsare significantlylarger(dueto the absence gles close to 90° (87–90°), similar to the other Pn(pyS)3
of N–Pn interactions). A very interesting feature of the compounds (Pn = P, As, Sb) with Bi–S bond lengths of
packing of the Pn(pyS) (Pn = P, As, Sb) molecules, which 2.70–2.74 Å. The Bi–N bond lengths of the chelating pyS
3
has briefly been mentioned for the structure of Sb(pyS) [30], ligands (2.66, 2.69 Å) are shorter than in the other Pn(pyS)3
3
is the occurrence of pairs of monomers within the crystal derivatives (featuring κ-S-bound pyS ligands with only
structure (selected metrical parameters Table 2). For these weak Pn···N contacts) and also than the third Bi–N bond
pairs, short Pn···Pn separations are observed (Pn = P: 3.84; (2.76 Å). The N–Bi–N angles are found in a quite narrow
As: 3.64; Sb: 3.66 Å, Figure 1, middle) which are below the range (with N atoms in the Bi core environment, involving
sum of the van-der-Waals radii of the Pn atoms (P: 3.90; As: N atoms of other asymmetric units; 113–122°) compared to
4
.10; Sb: 4.40 Å [43]). Intermolecular π–π stacking in- the trans S–Bi–N angles which are in a wider range (139–
teractions of the pyS ligands within the dimers (Figure 1, 162°). Considering the Bi atom to be located within the
right) stabilize this aggregation. The distances of the cen- planes spanned by the three N atoms in direct environment
troids of the pyridine hexagons (P: 3.56; As: 3.56; Sb: 3.65 Å) and by the three S atoms, the heavy pnictogen atom is
indicate significant non-covalent interactions of the het- shifted out of the N plane by only 0.20 Å, compared to
3
erocycles. The shortest Pn···Pn separation can be found for 1.62 Å from the S plane (opposite direction). Hence, the
3
Pn = As, indicating a pronounced interaction of the larger coordination environment is rather asymmetrical, sug-
pnictogen (As and Sb) with an enhanced tendency toward gesting the presence of a stereochemically active lone pair.
dispersion interactions in comparison to the P derivative. Alignment of the Bi atoms along a chain with bridging of
The poor solubility of the As derivative (in chloroform and the Bi⋅⋅⋅Bi contacts by one pyS ligand per Bi atom, and the
THF, videsupra)andthehighermeltingpoint(approx. 220°C absence of symmetry elements within the Bi(pyS) moieties
3
in this work; 201–204 °C in ref. [33]) in comparison to P(pyS)3 arising therefrom, give rise to this acentric unit cell setting.
(
1
approx. 120 °C) and Sb(pyS) (approx. 205 °C this work; The polymeric structure observed for Bi(pyS) is in contrast
3
3
93 °C in ref. [30]) is also indicative of the more pronounced to the monomeric structure found for the trimethylsilyl
attractiveforcesbetweentwoPn(pyS) moleculesforPn=As. derivative Bi(2-S-C H N-3-SiMe ) (Bi–S: 2.54–2.65 Å; Bi–N:
3
5
3
3 3

E. Wächtler et al.: Main group coordination chemistry
107
Table : Crystal data and parameters of data collection and structure refinement for the structures of Pn(pyS)
.(C ).

(Pn = P, As, Bi) and Al(pyS) ⋅


 
H

P(pyS)

As(pyS)

[Bi(κ -S,N-pyS)
μ-S,N-pyS)]

Al(pyS)

⋅ .(C H )
 
(
n
Chemical formula
C

H
N PS
  
C

H

AsN S

C

H

BiN S

C

H
Al

N S
 
M
r
.

.

.

.

Temperature, K
Crystal system
Space group
a, Å
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å
trigonal
Rꢀc
.()
= a
.()

trigonal
Rꢀc
.()
= a
.()

monoclinic
Cc
triclinic
Pꢀ
.()
.()
.()
.()
.()
.()
.()

.()
.()
.()



.()




.()

.()

.()

Z
F(), e




−

D
x
, g cm
.
.
.
.
.
.
.
.
μ, mm−


Crystal size, mm
. × . × .
./.

. × . × .
./.

. × . × .
./.

. × . × .
./.

T
min/Tmax
Measured reflections
Unique reflections




Observed reflections with [I >  σ(I)]




R
int
.
.
–
.
θ values, deg
(
.–.
.
h = −→
k = −→
l = −→

.–.
.
h = −→
k = −→
l = −→

.–.
.
h = −→
k = −→
l = −→

.–.
.
h = −→
k = −→
l = −→

sin θ/λ)max, Å−
Range of h, k, l

No. of reflections
No. of ref. parameters
No. of restraints










R [F >  σ(F )]
.
.
.
.

wR(F )
.
.
.
.
S
.
.
.
.
(
Δ/σ)max
.
–
./−.
.
–
./−.
<.
−.()
./−.
.
–
./−.
a
Flack x
Δρmax/Δρmin, e Å−

a
Absolute structure parameter.
Table : Selected Pn–R bond lengths (Å), R–Pn–R bond angles (deg) (R = S, N), distances of Pn···Pn contacts (Å) in comparison to the two-fold
van-der-Waals radius rvdW (Å) of Pn, and distances between the centroids CE (Å) of the pyS ligands for the compounds Pn(pyS) (Pn = P, As, Sb)
and selected parameters for Bi(pyS)


.
a
b
Pn
Pn–S
Pn···N
S–Pn–S
S–Pn–N
Pn···Pn
rvdW
CE···CE
P
As
Sb
.()
.()
.()
.()
.()
.()
.()
.()
.()
.()
.()
.()
.()
.()
.()
.
.
.
.
.
.
c
d
d
g
a,d
h
Bi
.
.


.()
.
–
e
f

.()
.()
a
b
c
d
S and N atoms of the same pyS ligand; van-der-Waals radii taken from ref. []; ref. []; average from the two similar chelating pyS ligands;
e
f
g
h
to κ-S-bound ligand; dative bond to κ-S-bound ligand of another monomeric unit; average from three similar angles; the Bi···Bi distance
equals the length of the crystallographic b axis.

1
08
E. Wächtler et al.: Main group coordination chemistry
3
Figure 1: Molecular structure of As(pyS) in the crystal. Ellipsoids set at the 50% probability level and hydrogen atoms omitted for clarity. Left:
As(pyS) molecule. Middle: Pn···Pn contacts between two molecules highlighted with red dashed line. View along [100]. Right: π–π stacking
3
between two pyS ligands highlighted with red dashed line. Symmetry operations: 1+y−x, 1−x, z (*), 1−y, −y+x, z (**), threefold rotational axis; x,
y, 0.5–z (‡), c glide plane + sixfold rotation-inversion.
2
.69–2.83 Å) in which the enhanced steric bulk of the li- SbClPh and unreacted SbCl . Upon attempted pyS sub-
2 3
gands does not allow for a close proximity of the ligands stitution (using NEt as supporting base) in THF, we found
3
[
31]. Regarding pyS-containing Bi(III) compounds, a poly- these impurities to cause significant problems regarding
2
meric structure was also found for [BiI(κ -S,N, µ-S-pyS) ]
crystallization and isolation of the final products as
2
n
(
Bi–S: 2.86–2.93 Å; Bi–N: 2.55) [44].
Sb(pyS) and Sb(pyS) Ph have similar solubilities (and this
3
2
Due to the fact that Ph/pyS mixed substituted pnic- is also true for the pair of SbPh and Sb(pyS)Ph ). Facing
3
2
togen compounds are also interesting starting materials for this issue, we have developed a synthetic protocol for the
the syntheses of TM complexes (see ref [22]), we studied the reaction of SbCl and SbPh in a 1:1 ratio. Along this route,
3
3
series of Sb(pyS) Ph
compounds (x = 3–0; x = 3 vide the amounts of remaining SbCl and SbPh in the SbCl Ph/
3 3 2
x
3–x
supra; x = 0 commercially available and well-studied). This SbClPh mixture are reduced to a minimum, and upon pyS
2
study could give comparative insights into the state of for Cl substitution both Sb(pyS) Ph and Sb(pyS)Ph are
2
2
bonding of the Pn atoms with varying substitution pat- obtained which can easily be separated by workup in hot
terns, which in case of this pnictogen can also be experi- hexane (solubility of the latter). This facile procedure gave
1
21
mentally assessed using Sb Mössbauer spectroscopy. Sb(pyS) Ph and Sb(pyS)Ph in good yields and purity
2
2
Whereas Sb(pyS)Ph had not previously been described, (Scheme 3).
2
the synthesis of Sb(pyS) Ph [starting from SbCl Ph and
Unfortunately, the crystals obtained for Sb(pyS)Ph2
2
2
Na(pyS)] was briefly reported and the crystal structure of were only of poor quality and did not allow for X-ray
the product determined, but with lack of details of the structure determination. Hence, we have optimized the
experimental procedure and incomplete characterization molecular structure of this compound by quantum chem-
[
33]. SbCl Ph and SbClPh can be prepared through the ical methods (see Supplementary Material available on-
2 2
reactions of SbCl with SbPh in a 2:1 or 1:2 ratio, respec- line). Even though a comparison of the calculated structure
3
3
tively [45]. However, these reactions do not afford pure of this compound (in vacuum) with the crystallographi-
products, with SbCl Ph e.g. being contaminated with cally determined structures of related compounds is,
2
Figure 2: Two representations of the molecular structure of the Bi(pyS)
including the κ-S-pyS ligand of another molecule as well as two symmetry equivalent Bi atoms; right: chain of five Bi(pyS)
crystallographic b axis with the pyS ligands outside the central asymmetric unit being reduced to the N–C–S atoms for clarity. Ellipsoids set on the
0% level and hydrogen atoms omitted. Symmetry operations: x, y−1, z (*); x, y+1, z (**); x, y−2, z (***); x, y+2, z (****); translations along the b axis.
3
coordination polymer; left: direct coordination environment of the Bi atom,
3
molecules along the
5

E. Wächtler et al.: Main group coordination chemistry
109
2 2
Scheme 3: One-pot synthesis of the compounds Sb(pyS) Ph and Sb(pyS)Ph .
strictly speaking, not meaningful in terms of bond lengths Table : Sb–S and Sb–C bond lengths (Å), Sb···N distances (Å) and
sum of the three R–Sb–R (R = S, C) angles (deg) of the compounds
Sb(pyS) Ph−x (x = –).
x
and angles, we include this structure into the comparative
discussion because the optimized structure of Sb(pyS)Ph2
is in accord with the general trends observed. The molec-
Compound
Sb–S
Sb–C
Sb···N
Σ(R–Sb–R)
ular structures of the compounds Sb(pyS) Ph3–x (x = 3–0; 3
x
a
Sb(pyS)
Sb(pyS)

.
./.
.
/
.
./.
.–.
.
./.
.
.
.
.
.
ref. [30, 31], 2 ref. [32], 0 ref. [46]) are depicted in Figure 3,
and the metrical parameters are summarized in Table 3.
b
c

Ph
Sb(pyS)Ph

The trigonal pyramidal SbS C motif in the structure of
d

2
SbPh
–
–
Sb(pyS) Ph is capped by the two N atoms in a way that they
2
a
b
c
d
Ref. []; ref. []; Molecular structure optimized in vacuum; ref.
].
donate electron density toward the Sb–S σ* orbitals. As a
result, the pyS ligands and the Sb atom are located almost
within a common plane. Due to the lower coordination
number ([2+3] coordination), the Sb···N contacts (2.63;
[
NMR time scale. The multiplet signals of the pyS ligand
protons (i.e. ddd patterns) could in most cases be resolved
and assigned. Due to the adjacent N atom, the H proton
resonance is shifted downfield (>8 ppm) and the J
2.73 Å) of this compound are shorter than in Sb(pyS)3
6
(
2.84 Å; [3+3] coordination). The donation of lone pair
3
H-5/H-6
electron density from N toward the Sb–S σ* orbital is not
coupling constant is reduced (around 5 Hz; 7–8 Hz for other
possible in Sb(pyS)Ph , (Sb–N separation 2.92 Å). The sum
3
2
JH-H). The change of the Pn atom leads to an up-field shift
of the R–Sb–R angles (R = S, C) increases with the number
of phenyl groups.
of all signals in the order of Pn = P, As, Sb. However, the Bi
compound does not follow this trend which might either be
explained by the different (averaged) pyS coordination or
the contribution of relativistic effects to the chemical shift
in case of this heavy atom.
2.2 NMR spectroscopy
Caused by the poor solubility of the As and Bi com-
1
3
1
The proton NMR spectra of the compounds Pn(pyS)3 pounds, C{ H} CP/MAS NMR spectra of the solids were
Pn = P, As, Sb, Bi) were recorded in CDCl , even though the recorded (Figure 5). In accord with the molecular structures
(
3
As and Bi compounds exhibit only very poor solubility. The in the crystal, the former reveals one set of pyS signals,
spectra show one set of signals of the four protons of the whereas the different coordination modes of the pyS li-
pyS ligand (Figure 4; the proton and carbon atoms are gands in Bi(pyS) lead to the detection of a complex set of
3
labeled according to Hantzsch/Widman with the positions signals.
1
2
3
3
4
4
31
1
N –C =S–(C –H )–(C –H )-…; [47, 48]). The Bi compound
The solution P{ H} NMR spectroscopic investigation
shows an averaged set of signals for the pyS ligands due to of P(pyS) reveals a signal at 91 ppm. Due to the shielding
3
the fast exchange between different pyS coordination caused by the N···P contacts, this signal is significantly
modes in solution (e.g. chelating and κ-S bound) on the more up-field shifted compared to that of P(SPh ) (131 ppm)
3
Figure 3: Molecular structures of the
compounds Sb(pyS) Ph3−x (x = 3: ref. [31]; 2:
x
ref. [32]; 1: molecular structure optimized in
vacuum; 0: ref. [46].

1
10
E. Wächtler et al.: Main group coordination chemistry
1
Figure 4: H NMR spectra of the compounds
Pn(pyS) (Pn = P–Bi) in CDCl
3
3
.
1
3
1
Figure 5: C{ H} CP/MAS NMR spectra
3
rot = 10 kHz) of As(pyS) and Bi(pyS) .
(ν
3
[
(
49]. In the NMR spectra of the compounds Sb(pyS) Ph
x = 3–0; Figure 6), the most pronounced effect is the down- difference in electronegativity between Pn and S causes the
close to 90°). For the pnictogen thiolates, the increasing
x
3–x
field shift of the ortho-proton resonance of the Ph sub- Pn–S BD-NLMO to be shifted toward S for the heavier pnic-
stituents with increasing x. CH···S contacts with the pyS togen (% Pn/% S contribution: P 38/60; As 34/65; Sb 27/71;
ligands, which should in general be accompanied by a Bi 19/77 av.). This is also reflected by the increasing natural
down-field shift, are the most likely cause [50].
charges (NC, Table 5) of Pn (P 0.56; As 0.80; Sb 1.14; Bi 1.30e),
which is mainly a result of a decreasing p-orbital population
(Np, P 2.62; As 2.35; Sb 2.01; Bi 1.71 e), in contrast to a slight
increase in s-orbital population (N , P 1.75; As 1.83; Sb 1.84; Bi
2
.3 NLMO calculations
s
1.94 e) of Pn. Regarding the s and p-orbital contributions
toward the Pn–S BD-NLMO, there is a noticeable tendency
toward an increasing s-orbital contribution to the Pn
LP-NLMO (% s/% p: P 79/21; As: 88/12; Sb: 89/11; Bi: 97/3)
and an increasing p-orbital contribution to the Pn–S
BD-NLMOs (% s/% p: P: 8/91; As, Sb: 5/95; 1/98), like it is
typically found in main group chemistry. For the compounds
Natural localized molecular orbital (NLMO) calculations of
the compounds Pn(pyS)3 (Pn = P, As, Sb, Bi) and
Sb(pyS) Ph (x = 3–0) were performed in order to elucidate
x
3–x
the changes of the bonding characteristics of the Pn atoms
induced by replacing the Pn atoms or modifying their ligand
patterns. The electronic structure of the Bi atom within the
coordination polymer was accessed by the calculation of a
trimeric model [Bi(pyS) ] , for which the data of the central
Sb(pyS) Ph (x = 3–0), the similar electronegativities of C
x
3–x
and S are reflected by comparable contributions of these
atoms toward the Sb–R bonds (R = C: 69–70%; R = S:
3
3
Bi atom is given and discussed. The NLMO analyses indicate
the presence of Pn lone pairs (LP-NLMOs) with predominant
s-orbital character and Pn–S and Sb–C bonds (BD-NLMOs)
with a predominant p-orbital contribution of Pn (Table 4).
This is in good agreement with the general observation of
70–72%; Sb contribution: 25–28%). However, significant
differences can be found for the s and p-orbital contribution
of Sb toward the Sb–R bonds: For the larger S atoms (and
hence longer Sb–R bonds), more favorable orbital overlaps
are realized with high p-orbital contributions of Sb (5–8% s;
trigonal pyramidal PnS units (featuring S–Pn–S angles
3

E. Wächtler et al.: Main group coordination chemistry
111
1
Figure 6: H NMR spectra of compounds
x 3
Sb(pyS) Ph3−x (x = 3–0) in CDCl .
9
2–95% p) and S (12–14% s; 86–88% p), whereas for R = C the [54]) and therefore, a reduction of the electron density at
s character of the Sb–R bonds is increased (Sb: 11–13% s; 87– the Sb nucleus results in less negative values for the isomer
9% p; C: 25–26% s; 74–76% p). Thus, for the compounds shift δ of the signal. The electron density at the Sb nucleus
Sb(pyS) Ph (x = 3–0) the Sb atoms contribute more s
8
x
3–x
electron density to their BD-NLMOs with decreasing x, and
therefore the p-orbital contribution to the Sb LP-NLMO is
enhanced (% s/% p, x = 3: 89/11; x = 2: 82/18; x = 1: 77/23;
x = 0: 68/32). This matches well with the observed molecular
Table : Selected data of the NLMO calculations of the compounds
Pn(pyS) (Pn = P, As, Sb, Bi) and Sb(pyS) Ph−x (x = –): percentage
of atomic contributions of Pn, S and C atoms to the NLMO for the lone

x
structures as the sum of R–Sb–R angles increases with the pair (LP)Pn and bonding (BD)Pn–R (R = S, C) NLMOs with hybrid
phenyl content (vide supra). The increasing NC of Sb in these composition ratios of the parent natural atomic orbitals (% s/% p) in
parentheses, energy E (kcal mol− ) of the strongest donor acceptor

compounds (x = 3–0, 1.14; 1.22; 1.25; 1.29 e) can be explained
interaction between LP(N) and Pn–S* calculated by second order
by the less effective charge compensation of the harder C
perturbation theory analysis.
donor compared to the softer S donor atom.
Finally, the energies of the N→Pn interactions can be
determined by second order perturbation theory analysis
compound
LP(Pn)
BD(Pn–C)
BD(Pn–S)
E
(N→Pn)
(
Table 4). They are in good agreement with the trends
P(pyS)

 P
/)
 As
(/)
 Sb
–
–
–
–
 P (/)
 S (/)
 As (/)
 S (/)
 Sb (/)
 S (/)
.
observed for the Pn···N distances (vide supra): For the
compounds Pn(pyS) , the energies increase with the As(pyS)
growth of the atomic number (Pn = P: 5; As: 9; Sb: 10; Bi: av.
2
pounds, they decrease in the order of x = 2 (av. 13), 3 (10)
and 1 (4 kcal mol ).
(
3
.
−
1
Sb(pyS)
Bi(pyS)
.
1 kcal mol ), and for the series of Sb(pyS) Ph
com-
3–x
x
(
/)
 Bi

 Bi (/) ., .
−
1
a
(
/)
 S (/)
.

 Bi (/)
 (/)
b

Sb(pyS)

Ph
 Sb  Sb (/)
/)  C (/)
 Sb  Sb (/)
(/)  C (/)
 Sb  Sb (/)
/)  C (/)
 Sb (/) ., .
 S (/)
2
.4 Mössbauer spectroscopy
(
Sb(pyS)Ph

 Sb (/)
 S (/)
–
.
121
The Sb Mössbauer spectra of the compounds Sb(pyS)x
Ph3–x (x = 2–0) were recorded and are depicted in Figure 7 SbPh

5
7
119
(
[
51–53]. In contrast to Fe or Sn Mössbauer spectroscopy,
1
21
the mean square radius of the isotope Sb in the ground
a

b
Average of the two similar Bi–S bonds to the κ -S,N-pyS ligand; to
2
state is smaller than in the excited state (i.e. negative <Δr > κ-S-pyS.

1
12
E. Wächtler et al.: Main group coordination chemistry
Table : Natural charges (e) and valence shell natural electron configuration (e) of the Pn atoms of the compounds Pn(pyS) (Pn = P, As, Sb, Bi)

and Sb(pyS)
x
Ph−x (x = –).
P(pyS)

As(pyS)

Sb(pyS)

Bi(pyS)


Sb(pyS) Ph
Sb(pyS)Ph

SbPh

NC
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
N
N
s
p
ρ(0) (in e a − ) can be deduced from the N5s/p-orbital pop- of the N→M interaction), we synthesized Al(pyS) and
3
13
0
3
ulations by the empirical equation:
determined its crystal structure (see Table 1 and Supple-
mentary Material available online for further details
including a plot of the molecular structure in the crystal). In
2
5
ρ(0) = 0.11 + 68.65N5s − 3.39N5p − 5.57N
s
−
1.00N5s
N
5p[55]
brief, also in Al(pyS) a chelating coordination mode of all
3
three pyS ligands is encountered. However, the smaller
The calculated values (derived from the N5s/p values given in group 13 element Al causes a change of the octahedral co-
Table 5) are summarized together with the parameters of the ordination from a fac to a mer configuration. As confirmed
1
21
1
13
data fitting procedure of the Sb Mössbauer spectra in Ta- by H and C NMR spectroscopy at T = −40 °C, this config-
ble 6. The magnitude of ρ(0) is in the expected range for uration is also favored in CDCl solution.
3
Sb(III) compounds [55] and follows the order SbPh3
<
Sb(pyS)Ph < Sb(pyS) Ph < Sb(pyS) . The δ = f[ρ(0)] plot (see
2
2
3
Supplementary Material available online) gives a good fit
with a correlation coefficient of 98%, indicating that the
pairs of calculated and measured electron density at the Sb
nucleus are in good agreement and thus supporting the
validity of the theoretical method applied. For the com-
3
Conclusions
With the results discussed herein, we present the first
comprehensive study of the synthesis and detailed analysis
(
X-ray diffraction, NMR spectroscopy, mp, elemental anal-
pounds Sb(pyS) Ph and Sb(pyS)Ph , the heteroleptic sub-
2
2
ysis, NLMO calculations) of the series of homoleptic pnic-
togen(III) pyridine-2-thiolates Pn(pyS) (Pn = P, As, Sb, Bi),
which is also the first report on the phosphorus compound.
The phosphorus and arsenic compounds were found to
crystallize isostructurally to the structure reported for
stitution pattern causes larger electronic quadrupole
3
−1
interactions (eQV ; 11.2(1) and 10.4(1) mm s , respectively)
ZZ
and larger asymmetry parameters η [0.41(3), 0.74(3)] in
comparison to those of the homoleptic compounds Sb(pyS)
3
−1
−1
[
eQVZZ 6.1(1) mm s ] and SbPh [eQV 9.3(1) mm s ], while
3 ZZ
Sb(pyS) , for which the presence of molecule pairs featuring
3
the slightly larger p-orbitalpopulation, i.e. the non-spherical
Pn···Pn contacts was already noticed. A comparison of those
structures revealed those contacts to be most pronounced
for Pn = As, which accounts for the higher melting point and
lower solubility in comparison with Pn = P and Sb. The low
electron density, of the latter also causes an enhancedeQVZZ
value compared to that of Sb(pyS)3.
solubility of Bi(pyS) , its poor crystal quality and the cell
3
2
.5 Comparison with group 13 analogues
parameters of a monoclinic structure close to the hexagonal
crystal system (and heavy twinning associated therewith)
While this study of group 15 compounds Pn(pyS) revealed hampered the crystallographic determination of this mo-
3
a systematic trend of increasing tendency toward N→Pn lecular structure. With optimized crystallization conditions,
2
coordination in the order Pn = P, As, Sb, Bi, a similar trend its structure was shown to be that of a [Bi(κ -S,N-pyS)
(μ-
2
1
3
for their group 13 analogues M (pyS) cannot be derived S,N-pyS)]
coordination polymer featuring two chelating
because of the lack of data for Al(pyS) . For M = In and Ga, and one κ-S bound pyS ligands. H NMR investigations,
3
n
1
3
1
3
octahedral coordination of the group 13 element has been however, suggest that discrete Bi(pyS)
reported, with the three pyS ligands adopting a fac sent in chloroform solution.
configuration [8–10]. In this regard, these two compounds
The electronic structures of the compounds Pn(pyS)
molecules are pre-
3
3
are related to the general N→Pn coordination motif, where were investigated by NLMO calculations, which detected
also a fac coordination in highly distorted octahedral ge- lone pair NLMOs with a high degree of s electron density
ometries was observed.
In order to probe whether the smaller Al atom would p character, which is in good agreement with the trigonal
cause a lowering of the coordination number (or weakening pyramidal PnS structural motif for all four compounds. In
located at Pn. The bondingPn–S NLMOsreveal predominant
3

E. Wächtler et al.: Main group coordination chemistry
113
121
x
Figure 7: Experimental (dots) and simulated (lines) Sb Mössbauer spectra of compounds Sb(pyS) Ph3−x (x = 3–0; 3 taken from [21]) relative
121m
−1
3
to Ba SnO at T = 5 K. Vertical line plotted at −10 mm s for comparison of the signal positions.

Table : Fitting parameters of the Sb Mössbauer spectra of
incorporating late transition metals which could feature
interesting metal–metal bonding situations, a topic which
we are currently investigating.
−

compounds Sb(pyS) Ph−x (x = –). Isomer shift δ (mm s ), elec-
x
tronic quadrupole interaction eQVZZ (mm s− ), experimental line
width Γ (mm s− ) and asymmetry parameter η; calculated electron
density at the Sb nucleus ρ() (a


1
3
−

For group 13 analogues M (pyS) , octahedral coordi-
3

) [].
1
3
13
nation of M is encountered even with M = Al. In this
1
3
Compound
δ
eQVZZ
Γ
η
ρ() series (M = In, Ga, Al), diminishing the atomic radius
causes a switch from fac to mer configuration of the octa-
a
Sb(pyS)
Sb(pyS)

−.()
−.()
−.()
−.()
.()
.()
.()
.()
.()
.()
.()
.()
/
.()
.()
/
.
hedral coordination sphere.

Ph
.
.
.
Sb(pyS)Ph

SbPh

a
Ref. [].
4
Experimental section
the row to lighter pnictogen central atoms (Bi, Sb, As, P), 4.1 General considerations
however, a slight degree of s/p hybridization was detected,
and the N→Pn interactions were found to decrease.
All reactions have been carried out under an atmosphere of
The set of Sb(pyS) Ph (x = 3–0) compounds was also dry argon (99.999%) using standard Schlenk techniques.
x
3–x
included in this study as examples of mixed substituted Solvents were dried by distillation over Na/benzophenone
Pn/pyS compounds. This stepwise substitution of pyS by (THF, diethyl ether), or Na (toluene, hexane, pentane) and
Ph causes an increasing s/p hybridization of the Sb atom, storage over molecular sieves 3 Å (CHCl , MeOH). Chem-
3
1
21
i.e. larger p electron density of the Sb lone pair NLMO. Sb icals were purchased from ABCR (AlEt , pySH, SbPh ),
3
3
Mössbauer spectroscopy proved to be an excellent exper- Acros Organics (PCl , SbCl ), AppliChem (NEt , further
3
3
3
imental probe for the calculated electronic properties of the distilled from Na/benzophenone) and Sigma-Aldrich
antimony atom in these compounds, represented in the (AsCl , Bi(NO ) ·5H O, n-BuLi).
3
3 3
2
1
21
δ = f[ρ(0)] plot (δ =
Sb Mössbauer isomer shift,
The melting points (not corrected) were determined on
ρ(0) = calculated electron density at the Sb nucleus [55]). a Polytherm A microscope (Wagner & Munz, Munich,
The set of the compounds Pn(pyS) are valuable starting Germany). Double determinations were carried out on a
3
materials for the synthesis of heterobimetallic compounds crystalline sample sealed in a glass capillary.

114
E. Wächtler et al.: Main group coordination chemistry
C/H/N/S elemental analyses were performed on a vario Samples were placed in 2.5 or 4 mm ZrO rotors and an
2
Micro cube analyzer (Elementar, Hanau, Germany) on MAS frequency of 10 kHz was applied. Spectra were
samples which had been dried under vacuum at room externally referenced to adamantane (38.5 ppm relative to
temperature. About 2 mg of the compound was placed in SiMe ). All NMR spectra were recorded at room tempera-
4
tin capsules and subjected to combustion in a flow of pure ture. The positions of the pyS signals are labeled accord-
1
2
3
3
4
4
5
oxygen at T = 1150 °C. The combustion gases were sepa- ing to Hantzsch/Widman: N –C =S–(C –H )–(C –H )–(C –
5
6
6
1
rated on adsorption/desorption columns and analyzed H )–(C –H ) [47, 48]. In most of the H NMR spectra, all the
quantitatively using a thermal conductivity detector.
proton couplings within the pyS ligand could be resolved,
i.e. each signal is split into three independent doublets
(
annotation as “d of dd”, multiplet m if coupling could
4
.2 X-ray structure determinations
not be resolved).
For single-crystal X-ray structure determination, a crystal of
the appropriate size was selected under inert oil and
mounted on a glass capillary, which was coated with sili-
cone grease. Data sets were collected on an IPDS-2(T)
diffractometer (STOE, Darmstadt, Germany) using graphite-
monochromatized MoKα radiation (λ = 0.71073 Å). In-
4
.4 NLMO calculations
All calculations were performed using GAUSSIAN09 [60].
The hydrogen atom optimization of the atomic coordinates
obtained from the X-ray diffraction analyses was per-
formed with DFT-PBEPBE def2-TZVPP. NBO6.0 was used
for the NBO/NLMO analyses [61]. DFT-B3LYP 6-311+G(d)
tensities were measured by ω scans. For P(pyS) , As(pyS)3
3
and Al(pyS) ·0.5C H , numerical absorption corrections
3
7 8
were applied by modeling the crystal surfaces based upon
the intensities of symmetry-equivalent reflections (XSHAPE
(
C, H, N, O, S, Cl, P) and SDD (As, Sb, Bi) basis sets were
applied including the second order Douglas-Kroll-Hess
scalar relativistic approach.
[56]). The structures were solved by Direct Methods (SHELXS
[
57]) and all non-hydrogen atoms were anisotropically
2
refined against F in full-matrix least-squares cycles (SHELXL
[
58]). Hydrogen atoms were (isotropically) included in the
4
.5 Mössbauer spectroscopy
refinement in geometrically idealized positions (riding
model). Further details of the structure determinations of
1
21
For the recording of the Sb Mössbauer spectra, the sam-
Bi(pyS) and Al(pyS) ·0.5C H , including a plot of the mo-
3
3
7
8
−2
ple (ideally containing 10 mg cm Sb) was ground in a
mortar and placed in PMMA containers of about 2 cm in
diameter. The spectra were recorded at 5 K in transmission
geometry. Isomer shifts are given against Ba SnO3,
which was used as a γ-radiation source. The WINNORMOS for
IGOR program package was used for data fitting [62].
lecular structure of the latter, are given in the Supplemen-
tary Material available online.
CCDC 1543907 [P(pyS) ], 1543895 [As(pyS) ], 2038356
3
3
121m
[
Bi(pyS) ] and 2038357 [Al(pyS) ·0.5C H ] contain the
3 3 7 8
supplementary crystallographic 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.
4
.6 Synthetic part
4
.3 NMR spectroscopy
4.6.1 P(pyS)3
Solution NMR spectra were acquired on an ASCEND 400 or pySH (1.00 g, 9.00 mmol) and NEt (1.37 g, 13.3 mmol) were
3
AVANCE 500 spectrometer (Bruker BioSpin, Rheinstetten, dissolved in THF (15 mL) at 0 °C. Afterwards, PCl (453 mg,
3
Germany) from samples in 5 mm glass tubes using CDCl3 3.30 mmol) was slowly added via syringe, causing the
(
99.8%, stabilized by Ag foil) as a solvent which has been formation of a white precipitate. This mixture was stirred
dried by storage over 3 Å molecular sieves. Chemical shifts for 2 h at this temperature. Afterwards, the HNEt Cl pre-
3
are given in ppm. The spectra were internally referenced to cipitate was filtered off and washed with THF (2 × 3 mL).
1
13
1
residual solvent signals ( H: 7.26 ppm; C{ H} 77.16 ppm, The volume of the combined filtrate and washings was
3
1
1
relative to SiMe ) [59], P{ H} was externally referenced reduced under vacuum until crystallization of a white solid
4
1
3
1
against 85% H PO . The solid state C{ H} CP/MAS NMR commenced (about 5 mL). This suspension was warmed
3
4
spectra were recorded on a AVANCE III HD 400WB slightly upon which a clear solution was obtained. The
spectrometer (Bruker BioSpin, Rheinstetten, Germany). mixture was then stored at T = −21 °C for 3 days, giving

E. Wächtler et al.: Main group coordination chemistry
115
colorless crystals (suitable for X-ray diffraction analysis), washings gave rise to the formation of colorless crystals of
which were isolated by decantation, washed with diethyl the product. These crystals were isolated by decantation,
ether (2 × 2 mL) and dried under vacuum. Yield: 774 mg washed with diethyl ether (2 × 2 mL) and dried under
1
(
2.14 mmol, 71%). – H NMR (CDCl , 500.13 MHz): δ = 7.05 (d vacuum. Yield: 0.50 g (1.10 mmol, 73%).
3
3
4
of dd, J
= 7.3/5.0 Hz, J
= 8.0 Hz, 3H, H-3 pyS), 7.54 (d of dd, J
= 1.9 Hz, 3H, H-4 pyS), 8.33 ppm (m, 3H, H-6 A solution of pySH (1.00 g, 9.00 mmol) in THF (20 mL) was
pyS). – C{ H} NMR (CDCl , 125.77 MHz): δ = 120.6 (br, C-5 treated with n-BuLi (3.6 mL, 2.5 M in hexanes, 9.00 mmol)
= 1.0 Hz, 3H, H-5 pyS), 7.46
H–H
H–H
3
3
(m, J
= 8.0/ 4.6.3.2 Method b
H–H
H–H
4
7
.3 Hz, J
H–H
1
3
1
3
pyS), 124.7 (br, C-3 pyS), 136.6 (C-4 pyS), 149.5 (br, C-6 pyS), at −21 °C. After 15 min, solid SbCl (685 mg, 3.00 mmol) was
3
31
1
1
57.5 ppm (br, C-2 pyS). – P{ H} NMR (CDCl , 202.46 MHz): added and the mixture was stirred at this temperature for
3
δ = 91.1 ppm. – M. p. 117–121 °C. – C H N PS (361.45): 2 h after which it was allowed to attain room temperature.
15
12
3
3
calcd. C 49.84, H 3.35, N 11.63; found C 49.35, H 3.50, N The solvent was removed under vacuum, and the solid
1.54. residue was suspended in MeOH (10 mL) and stirred for
0 min at ambient temperature. Afterwards, the product
1
3
4
.6.2 As(pyS)3
was filtered off, washed with MeOH (3 × 2 mL) and dried
1
under vacuum. Yield: 1.25 g (2.76 mmol, 92%). – H NMR
3
A solution of pySH (1.50 g, 13.5 mmol) and NEt (2.00 g, (CDCl , 500.13 MHz): δ = 6.93 (d of dd, J
= 7.3/5.1 Hz,
3
3
H–H
4
3
1
9.8 mmol) in CHCl3 (20 mL) was treated with AsCl3
JH-H = 1.1 Hz, 3H, H-5 pyS), 7.25 (m, J
= 8.0 Hz, 3H, H-3
= 1.8 Hz, 3H, H-4
H–H
H-H
3
4
(816 mg, 4.50 mmol) at room temperature, causing the pyS), 7.47 (d of dd, J = 8.1/7.3 Hz, J
H-H
3
4
formation of a white solid. The solution was stirred for 2 h pyS), 8.09 ppm (d of dd, J
and then filtered and washed with CHCl (3 × 2 mL). This
= 5.1 Hz, J
= 1.8 Hz,
H-H
H–H
5
13
1
JH-H = 1.0 Hz, 3H, H-6 pyS). – C{ H} NMR (CDCl ,
3
3
crude product was recrystallized from boiling toluene 100.62 MHz): δ = 118.7 (C-5 pyS), 124.9 (C-3 pyS), 136.9 (C-4
37 mL), and crystals suitable for X-ray crystallography pyS), 147.1 (C-6 pyS), 162.5 ppm (C-2 pyS). – M. p. 203–
(
formed overnight by slow cooling to room temperature. 206 °C. – C H N S Sb (452.23): calcd. C 39.84, H 2.67, N
15 12 3 3
The supernatant was removed by decantation, and the 9.29; found C 40.00, H 2.81, N 9.14.
product was washed with toluene (2 × 2 mL) and pentane
(
(
(
(
2 × 2 mL) and dried under vacuum. Yield: 1.40 g 4.6.4 Bi(pyS)3
1
3.45 mmol, 77%). – H NMR (CDCl , 400.13 MHz): δ = 6.98
3
3
4
d of dd, J
= 7.4/5.0 Hz, J
= 1.1 Hz, 3H, H-5 pyS), 7.30 pySH (250 mg, 2.25 mmol) and NEt (400 mg, 3.95 mmol)
= 8.0 Hz, 3H, H-3 pyS), 7.49 (d of dd, J
H–H
H–H
3
3
3
m, J
= 8.0/ were dissolved in MeOH (20 mL) and solid Bi(NO ) ·5H O
H–H
H–H 3 3 2
4
7
.4 Hz, J
= 1.9 Hz, 3H, H-4 pyS), 8.20 ppm (m, 3H, H-6 (364 mg, 0.75 mmol) was added. The resulting yellow sus-
H–H
13
1
pyS). – C{ H} MAS NMR (100.67 MHz, νrot = 10 kHz): pension was stirred for 4 h at ambient temperature. There-
δ = 119.6 (C-5 pyS), 122.8 (C-3 pyS), 136.3 (C-4 pyS), 149.3 (C- after, the solid was filtered off, washed with MeOH (2 × 4 mL)
6
pyS), 161.2 ppm (C-2 pyS). – M. p. 219–223 °C. and dried under vacuum. Yield: 360 mg (667 µmol, 89%).
1
3
–
C H AsN S (405.40): calcd. C 44.44, H 2.98, N 10.37; – H NMR (CDCl , 500.13 MHz): δ = 6.95 (d of dd, J
= 7.3/
15
12
3
3
3
H–H
4
3
found C 44.35, H 2.97, N 10.29. The product, once isolated, 5.2 Hz, J
showed very poor solubility in common organic solvents
= 1.0 Hz, 3H, H-5 pyS), 7.15 (d of dd, J
H–H
H–
4
5
= 8.1 Hz, J = 1.0 Hz, J
= 1.0 Hz, 3H, H-3 pyS), 7.52 (d
= 1.8 Hz, 3H, H-4 pyS),
= 5.2 Hz, J
H
H-H
H–H
3
4
(such as CHCl , CH Cl or THF), insufficient in order to re- of dd, J
= 8.1/7.3 Hz, J
3
2
2
H–H
H–H
13
1
3
4
5
cord a C{ H} NMR spectrum in solution.
8.19 ppm (d of dd, J
= 1.8 Hz, J
H–H
H–H H–H
13
1
=
1.0 Hz, 3H, H-6 pyS). – C{ H} MAS NMR (100.67 MHz,
νrot = 10kHz):δ = 120.0, 127.5, 123.1, 128.5, 130.8, 138.0, 139.6,
43.2, 145.3, 147.8, 163.5, 166.1 ppm. – M. p. 234–236 °C.
– C H BiN S (539.45): calcd. C 33.40, H 2.24, N 7.79; found
4
4
.6.3 Sb(pyS)3
1
.6.3.1 Method a
15
12
3 3
The compounds pySH (0.50 g, 4.50 mmol) and NEt (0.68 g, C 33.44, H 1.98, N 7.45. The solubility of this compound at
3
13
1
6
.72 mmol) were dissolved in THF (10 mL) and the solution room temperature is not sufficient to record a C{ H} NMR
was cooled to 0 °C. To this solution, solid SbCl (0.34 g, spectrum in solution.
3
1
.50 mmol) was added, and the mixture was stirred and
allowed to slowly attain room temperature. After 1 h, the 4.6.5 Sb(pyS) Ph and Sb(pyS)Ph2
2
triethylamine hydrochloride precipitate was filtered off
and washed with THF (2 × 2 mL). Afterwards, gas phase Both compounds were prepared in a one-pot reaction
diffusion of diethyl ether into the combined filtrate and starting from a mixture of SbCl and SbPh (molar ratio 1:1,
3
3

116
E. Wächtler et al.: Main group coordination chemistry
thus furnishing equal amounts of SbCl Ph and SbClPh ). Sb(pyS)Ph showed a high mosaicity (broad diffraction
2
2
2
The final products can be easily separated by stirring of the spots) which hampered the determination of the crystal
product mixture in hot hexane (Sb(pyS) Ph insoluble, structure.
2
Sb(pyS)Ph soluble). SbCl (1.00 g, 4.38 mmol) and SbPh
3
2
3
(
1.55 g, 4.38 mmol) were heated to 150 °C for 3 h in a Schlenk
4.6.6 Al(pyS)3
tube with stirring, whereupon a brown oil formed. After
cooling to room temperature, some of this oily material
pySH (0.50 g, 4.50 mmol) was dissolved in THF (30 mL) and
(
SbCl Ph and SbClPh , 1.74 g, 3.00 mmol each) was slowly
2 2
cooled to −78 °C. At this temperature, a solution of AlEt in
3
added to a stirred solution of pyridine-2-thiol (1.00 g,
.00 mmol) and NEt (1.40 g, 13.8 mmol) in THF (40 mL) via
hexane (10%, 1.89 g, 1.65 mmol) was slowly added via sy-
ringe and stirring at −78 °C was continued for 4 h. After-
wards, the mixture was allowed to warm to room
temperature and further stirred for 1.5 h. Then, the solvent
of the yellowish solution was evaporated under vacuum
and the solid residue was recrystallized from hot toluene
9
3
syringe, upon which a white suspension formed. This
suspension was stirred at 0 °C for 1 h and the mixture was
filtered. The HNEt Cl on the filter was washed with THF (3 ×
3
4
mL) and discarded. The solvent of the combined filtrate
and washings was completely removed under vacuum, and
the solid off-white residue was suspended in hexane
(
6 mL). Almost colorless (slightly yellow/beige) crystals of
Al(pyS) ·0.5C H suitable for single-crystal X-ray diffrac-
tion were isolated by decantation, washed with toluene
(2 mL) and dried under vacuum. Yield: 495 mg (1.23 mmol,
3
7 8
(
50 mL) and stirred at 50 °C for 30 min. The crude
Sb(pyS) Ph was then filtered off the reaction mixture,
2
washed with hexane (2 × 5 mL) and recrystallized from
8
2%). Upon further drying prior to elemental analysis,
boiling THF (10 mL). From the Sb(pyS)Ph -containing
2
the crystals lost some solvent of crystallization, and
the C, H, N contents found correspond to the composition
Al(pyS) ·0.3C H .
filtrate, about 45 mL of hexane were distilled off, leading to
the formation of colorless needles of Sb(pyS)Ph upon
2
–
C H AlN S ·0.3C H
(385.10):
3
7
8
15 12
3
3
7 8
cooling to room temperature. This compound was isolated
by decantation, washed with cold hexane (2 × 3 mL) and
dried under vacuum.
calcd. C 53.33, H 3.77, N 10.91; found C 52.75, H 4.04, N
27
1
1
0.25. – Al{ H} NMR (CDCl , 104.26 MHz): δ = 22.7 ppm.
3
1
13
1
The H, C{ H} NMR data including variable-temperature
experiments are listed in the Supplementary Material
available online.
4
.6.5.1 Sb(pyS) Ph
2
1
Yield: 690 mg (1.64 mmol, 55%). – H NMR (400.13 MHz,
3
4
CDCl ): δ = 6.90 (d of dd, J
= 7.3/5.2 Hz, J
= 1.0 Hz,
3
H–H
H–H
2
H, H-5 pyS), 7.22 (m, 1H, Ph ), 7.25–7.29 (m, 4H, Phmeta, 5 Supporting information
para
3
4
H-3 pyS), 7.42 (d of dd, J
H-4 pyS), 8.01 (m, 2H, Ph
= 8.3/7.2 Hz, J
= 1.7 Hz, 2H,
H–H
H–H
3
), 8.17 (m, J
= 5.2 Hz, 2H, Further data on the NMR spectroscopic characterization and
H–H
ortho
13
1
H-6 pyS). – C{ H} NMR (100.62 MHz, CDCl ): δ = 118.6 (C-5 the crystal structure determination of Al(pyS) , details of data
pyS), 124.7 (C-3 pyS), 128.6 (Phmeta), 128.9 (Phpara), 134.0 collection and structure refinement of [Bi(κ -S,N-pyS)
3
3
2
2
(
Phortho), 136.6 (C-4 pyS), 147.1 (C-6 pyS), 147.5 (Phipso), (μ-S,N-pyS)] , details of the quantum chemical calculations
n
1
61.1 (C-2 pyS). – M. p. 186–190 °C. – C H N S Sb (419.18): of Sb(pyS)Ph2 and δ = f[ρ(0)] plot for the compounds
16 13 2 2
calcd. C 45.84, H 3.13, N 6.68; found C 45.70, H 3.12, N 6.70. Sb(pyS) Ph (x = 3–0) can be found as supplementary ma-
x
3−x
terial in the online version (https://doi.org/10.1515/znb-2020-
171).
0
4
.6.5.2 Sb(pyS)Ph2
1
Yield: 500 mg (1.29 mmol, 43%). – H NMR (500.13 MHz,
CDCl ): δ = 6.95 (d of dd, J
1
3
4
= 7.3/5.0 Hz, J
= 1.0 Hz, Acknowledgments: Dr. Erica Brendler is acknowledged for
3
H–H
H–H
1
3
H, H-5 pyS), 7.32-7.38 (m, 7H, Phmeta/para/H-3 pyS), 7.44 (d recording the solid-state C NMR spectra of As(pyS) and
3
3
4
of dd, J
= 8.0/7.3 Hz, J
= 1.9 Hz, 1H, H-4 pyS), 7.66 Bi(pyS)3.
H–H
= 5.0 Hz, 1H, H-6 pyS). – Author contributions: All the authors have accepted
H–H
H-H
3
(
m, 4H, Ph
), 8.21 (m, J
ortho
1
3
1
C{ H} NMR (125.75 MHz, CDCl ): δ = 119.2 (C-5 pyS), 123.5 responsibility for the entire content of this submitted
3
(
(
C-3 pyS), 128.8 (Phmeta), 128.9 (Phpara), 135.7 (Phortho), 136.1 manuscript and approved submission.
C-4 pyS), 141.1 (Phipso), 148.8 (C-6 pyS), 159.6 (C-2 pyS). – Research funding: None declared.
M. p. 83–87 °C. – C H NSSb (386.13): calcd. C 52.88, H Conflict of interest statement: The authors declare no
17 14
3
.65, N 3.63; found: C 52,87, H 3.69, N 3.71. The crystals of conflicts of interest regarding this article.

E. Wächtler et al.: Main group coordination chemistry
117
2
2
8. Gericke R., Wagler J. Inorg. Chem. 2020, 59, 6359–6375.
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