Role of the Trichlorostannyl Ligand in Tin–Ruthenium Arene Complexes: Experimental and Computational Studies

Article abstract of DOI:10.1002/ejic.201700098

A set of neutral and ionic ruthenium arene trichlorostannyl complexes are reported herein. The tin(II) compounds L¹SnCl {1; L¹ = [2-(CH₂NEt₂)-4,6-(tBu)₂C₆H₂]^–} and [L²SnCl][SnCl₃] {2; L² = 2,6-[(CH₃)C=N(C₆H₃-2,6-iPr₂)₂]C₅H₃N} showed a rather different reactivity towards the ruthenium complex [(η⁶-cymene)RuCl]₂(η-Cl)₂. As a consequence, the neutral complex [Ru(η⁶-cymene)(L¹SnCl)Cl₂] (4) and the ionic compound [L²SnCl][Ru(η⁶-cymene)(SnCl₃)₂Cl] (8) were isolated. The insertion reaction of 4 with SnCl₂ provided the neutral trimetallic ruthenium complex [Ru(η⁶-cymene)(L¹SnCl)(SnCl₃)Cl] (6). Analogous ruthenium complexes [Ru(η⁶-cymene)(L³PPh₂)Cl₂] (5) and [Ru(η⁶-cymene)(L³PPh₂)(SnCl₃)Cl] (7) containing the phosphane ligand L³PPh₂ {3; L³ = [2,6-iPr₂-(C₆H₃)NH]^–} were also prepared to evaluate the donor–acceptor strength of the tin(II)- and phosphorus-containing ligands. The structural characterization and DFT calculations of the above-mentioned complexes suggest a strong influence of the [SnCl₃]^– moiety on the Ru–E interaction (E = Sn, P). The influence of the trichlorostannyl ligand on the Ru–E interaction in the complexes 4–7 was further evaluated by means of a distortion/interaction analysis.

Full text of DOI:10.1002/ejic.201700098

A Journal of
Accepted Article
Title: The Role of the Trichlorostannyl Ligand in Tin-Ruthenium Arene
Complexes: Experimental and Computational Studies
Authors: Roman Jambor, Miroslav Novák, Marek Bouška, Libor Dostál,
Michael Lutter, Klaus Jurkschat, Jan Turek, Frank De Proft,
and Zdenka Růžičková
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700098
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10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
The Role of the Trichlorostannyl Ligand in Tin-Ruthenium Arene
Complexes: Experimental and Computational Studies
Miroslav Novák,[a] Marek Bouška,[a] Libor Dostál,[a] Michael Lutter,[b] Klaus Jurkschat,[b] Jan Turek,[c]*
Frank De Proft, [c] Zdeňka Růžičková,[a] Roman Jambor[a]*
Abstract: A set of neutral and ionic ruthenium arene trichlorostannyl
complexes is reported. The tin(II) compounds L1SnCl (1, L1 = [2-
dimethoxymethane,[5e] carbene-carbene coupling reactions[5f] or
the methylation of alkylamines.[5g] Apart from the
cyclopentadienyl ruthenium trichlorostannyl complexes, only a
few arene ruthenium complexes containing trichlorostannyl
ligands have been reported so far (Figure 1A). [6]
(CH2NEt2)-4,6-(tBu)2C6H2]–) and [L2SnCl][SnCl3] (2, L2
= 2,6-
[(CH3)C=N(C6H3-2,6-iPr2)2]C5H3N) show a rather different reactivity
towards the ruthenium complex [(6-cymene)RuCl]2(-Cl)2. As a
consequence, the neutral complex [Ru(6-cymene)(L1SnCl)Cl2] (4)
and the ionic compound [L2SnCl][Ru(6-cymene)(SnCl3)2Cl] (8) were
isolated. The insertion reaction of 4 with SnCl2 provided the neutral
trimetallic ruthenium complex [Ru(6-cymene)(L1SnCl)(SnCl3)Cl] (6).
Analogous ruthenium complexes [Ru(6-cymene)(L3PPh2)Cl2] (5)
and [Ru(6-cymene)(L3PPh2)(SnCl3)Cl] (7) containing the phosphane
ligand L3PPh2 (3, L3 = {2,6-iPr2-(C6H3)NH}–) were also prepared in
order to evaluate the donor-acceptor strength of the tin(II)- and
phosphorus-containing ligands . The structural characterization and
DFT calculations of the above-mentioned complexes suggest a
strong influence of the [SnCl3]– moiety on the Ru-E interaction (E =
Sn, P). The influence of the trichlorostannyl ligand on the Ru-E
interaction in the complexes 4 - 7 was further evaluated with a
distortion/interaction analysis.
NEt2
iPr
iPr
iPr
tBu
Sn
Ru
Ru-
Ru
Cl
SnCl3
SnCl3
Cl
SnCl3
X
R
Ph3
P
Cl3Sn
tBu
N
SnCl3
iPr
iPr
L1SnCl (1)
R = P(OMe)3, PhCN
X = Cl, SnCl3
Sn+
Cl
[SnCl3]-
N
iPr
N
H3
C
Ru
Ru+
NHPPh2
Ru+
NH
Cl
2SnCl3
SnCl3
S
SnCl3
NCPh
PhCN
PPh
S
iPr
[L2SnCl]+ [SnCl3]- (2)
Ph
iPr
Ph3
P
L3PPh2 (3)
B
A
Figure 1. (A) Examples of arene ruthenium complexes containing the
trichlorostannyl moiety; (B) Donor ligands used in this study.
While the reaction of the anhydrous SnCl2 with an appropriate
arene ruthenium chloride complex yielding the corresponding
trichlorostannyl derivatives is rather straightforward, the
particular role of the SnCl3 moiety in these complexes has not
been clearly specified. Nevertheless, it is believed that its high -
acceptor character removes the electron density from the
ruthenium atom, which enhances its ability to interact with
organic substrates.[7]
Therefore, we decided to investigate tin containing arene
ruthenium complexes in more detail. Both the C,N-chelated
stannylene L1SnCl (1), where L1 is [2-(CH2NEt2)-4,6-(tBu)2C6H2]–,
and the salt [L2SnCl][SnCl3] (2), where L2 is 2,6-[(CH3)C=N(C6H3-
2,6-iPr2)2]C5H3N,[8a] containing a N,N,N-chelated tin(II) cation
were used as potential donor ligands, where the tin atom can
coordinate to the ruthenium atom via the lone pair of electrons.
Similarly, amidophosphane L3PPh2 (3), where L3 is {2,6-iPr2-
(C6H3)NH}–, was recently applied to synthesize the analogous
Ru complex [Ru(6-cymene)(L3PPh2)Cl2],[9] and therefore this
compound was used in this study to compare the donor ability of
the tin and phosphorus atoms in appropriate arene ruthenium
complexes (Figure 1B). Moreover, insertion reactions of the
above-mentioned ruthenium complexes stabilized by various
donor ligands with SnCl2 were also studied.
Introduction
Ru/Sn based alloys have shown efficient catalytic properties in
particular in the hydrogenation of various organic substrates.[1]
A
binary RuCl3/SnCl2 composite catalyst was found as an
interesting catalytic system for the dehydrogenating conversion
of methanol to acetic acid.[2] As a result, the syntheses and
structural studies of well-defined Ru–Sn complexes are of
current interest. Despite of the well-established insertion
reaction of tin dichloride into metal–halogen bonds,[3] the
reaction of SnCl2 with ruthenium derivatives has only been
observed scarcely.[4] Among these, the cyclopentadienyl
ruthenium
trichlorostannyl
complexes
[(5-
C5H5)(phosphane)2Ru(SnCl3)] have been synthesized[5] and
tested as catalysts for the preparation of methyl acetate from
methanol,[5b-d] selective electrochemical oxidation of methanol to
[a]
Department Department of General and Inorganic Chemistry,
Faculty of Chemical Technology, University of Pardubice, 53210
Pardubice, Czech Republic,
E-mail: roman.jambor@upce.cz, http://www.upce.cz
Lehrstuhl fꢀr Anorganische Chemie II, Technische Universitꢁt
Dortmund, 44221 Dortmund, Germany
Eenheid Algemene Chemie (ALGC), Member of the QCMM VUB-
UGent Alliance Research Group, Vrije Universiteit Brussel,
Pleinlaan 2, 1050 Brussels, Belgium;
[b]
[c]
As a result of their different reactivity, the present paper reports
the syntheses, structural characterization and DFT calculations
of the bi- and trimetallic neutral arene ruthenium complexes with
one trichlorostannyl ligand, as well as the anionic arene
ruthenium complex containing two trichlorostannyl ligands.
E-mail: jturek@vub.ac.be, http://we.vub.ac.be/~algc/index.html
Crystalographic details and NMR data re given in Supporting
information.
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10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
Results and Discussion
678 Hz), clearly demonstrating the presence of the SnCl3
substituent in both complexes. The values are close to those
found for [(6-cymene)Ru(PPh3)(SnCl3)(Cl)] (–205.8, 704 Hz).[6b]
In addition, the 119Sn NMR spectrum of 6 also showed a signal
at 110.1, that corresponds to the coordinated L1SnCl moiety.
The downfield shift of this signal from 14.6 in 4 to 110.1 in 6
can be thus attributed to the insertion of the SnCl2 into the Ru-Cl
bond. The latter also suggests a strong influence of the SnCl3
moiety on the L1SnCl coordination ability in the parent Ru
complexes. The 19Sn NMR spectrum of 6 revealed also second
set of signals with lower intensity at –191.2 and 143.9 of
second diastereomer in solution. The 31P{1H} NMR spectrum of
7 revealed a signal at 79.4 flanked with satellites (2J(119Sn, 31P)
= 665 Hz) being shifted downfield in comparison with the parent
compound 5 containing Ru-Cl bonds only (57.9).[9]
Synthesis and NMR studies of Ru complexes
The reaction of L1SnCl (1)[10] and L3PPh2 (3)[9] with [(6-
cymene)RuCl]2(-Cl)2 gave the corresponding complexes
[Ru(6-cymene)(L1SnCl)Cl2] (4) and [Ru(6-cymene)(L3PPh2)Cl2]
(5),9 respectively (Scheme 1). Furthermore, the insertion of
SnCl2 into the Ru-Cl bond in 4 and 5 provided the trimetallic and
bimetalic
neutral
ruthenium
(6)
complexes
and
[Ru(6-
[Ru(6-
cymene)(L1SnCl)(SnCl3)Cl]
cymene)(L3PPh2)(SnCl3)Cl] (7) containing one trichlorostannyl
ligand (Scheme 1). The insertion reaction into the remaining Ru-
Cl bond in 6 and 7 by an excess of SnCl2 did not proceed.
iPr
iPr
iPr
In contrast to the reactivity of the stannylene 1, the treatment of
[L2SnCl][SnCl3] (2),[8] as a possible tin containing donor ligand,
with [(6-cymene)RuCl]2(-Cl)2 and [(6-benzene)RuCl]2(-Cl)2
gave the ionic ruthenium complexes [L2SnCl][Ru(6-
cymene)(SnCl3)2Cl] (8) and [L2SnCl][Ru(6-benzene)(SnCl3)2Cl]
(9), respectively, where an arene ruthenium anion contains two
trichlorostannyl ligands (Scheme 2).
2 eq. L1SnCl (1) or L3PPh2 (3)
SnCl2
THF
Ru
Cl
Ru
Cl
Ru
Cl
SnCl3
R
Cl
Cl
R
Cl
THF
Cl
Ru
6: R = L1SnCl
7: R = L3PPh2
4: R = L1SnCl
5: R = L3PPh2
iPr
Scheme 1. Synthesis of the neutral arene ruthenium complexes 4 - 7.
-
CH2Cl2
6-arene)
The present compounds are orange (6, 7) to red (4) crystalline
[L2SnCl]+
Ru
2
[L2SnCl]+[SnCl3]- + 1/2 [(6-arene)RuCl]2(-Cl)2
materials, which are well soluble in chlorinated solvents.
- [L2SnCl]+ Cl-
Cl
Cl3Sn
1
2
SnCl3
The H NMR spectrum of 4 showed an AB spin system for the
NCH2 protons at A 4.04 and B 4.18 with JAB being
approximately 7 Hz. The ring protons of the cymene ligand in 4
constitute an AA´BB´ spin system at A 5.52, A´ 5.57, B 5.67
and B´ 5.71 with JAB being approximately 5 Hz as the
consequence of asymmetric tin atom. Accordingly, the 13C NMR
spectrum showed for the cymene moiety two signals at  82.5
and 84.1 ppm for the C2,6 and two signals at  84.4 and 84.8
ppm for the C3,5 carbon atoms. The 119Sn NMR spectrum of 4
showed one signal at -14.6 being shifted upfield relative to 1
(269.4).[10] The NMR data obtained for compound 5 agree well
with the data published earlier.[9] However, the molecular
structure of 5 was not yet determined (see discussion below).
8: arene = iPr-C6H4-Me
9: arene = C6H6
Scheme 2. Synthesis of the anionic ruthenium complexes 8 and 9
The 1H NMR spectrum of 8 showed the ring protons of the
cymene ligand resonating as two doublets at 5.77 and 5.87
ppm. For 9, a singlet resonance of the benzene protons was
observed at  5.83 ppm. The 119Sn NMR spectra showed one
signal at –160.2 for 8 and at –151.1 for 9, demonstrating the
equivalency of both SnCl3 substituents in the arene ruthenium
anions, while a second signal at –423.1 (for 8) and –423.0
(for 9) unambiguously validates the existence of the [L2SnCl]+
cation.[8] The former signals are shifted downfield in comparison
to the signals of the SnCl3 moieties in the neutral complexes 6
and 7. They are close to the values found in the related arene
ruthenium anions (ranging from –164.0 to –167.2 ppm).[6a] The
latter, upfield shifted, signals are close to the value found for the
[L2SnCl]+ moiety (–423.1).[8a] The ionic character of 9 and the
formation of [Ru(6-benzene)(SnCl3)2Cl]– anion has been also
corroborated by the ESI/MS spectrum (positive mode), showing
a mass cluster centered at m/z = 636.2. It is assigned to the
[L2SnCl]+ cation. In the negative mode, a mass cluster centered
at m/z = 666.5 was observed and assigned to the [Ru(6-
benzene)(SnCl3)2Cl]– anion.
1
The H NMR spectrum of 6 showed an AX spin system for the
NCH2 protons at A 3.89 and X 4.25 with JAB being
approximately 11 Hz. In the 1H NMR spectra of 6 and 7, the ring
protons of the cymene ligand constitute a well-resolved AA´BB´
spin system at A 5.80, A´ 5.88, B 6.07 and B´ 6.12 with JAB
being approximately 5 Hz in 6 (similarly 5.24, 5.44, 5.79 and
6.09 in 7) as a result of the three different substituents on the
Ru(II) atom. In addition, the 1H NMR spectrum of 6 revealed also
second set of signals with lower intensity (an AX spin system for
the NCH2 protons at A 3.89 and X 4.39 with JAB = 15 Hz and
AA´BB´ spin system at A 5.94, A´ 5.96, B 6.05 and B´ 6.02
with JAB = 4 Hz of the ring protons of the cymene ligand) proving
the existence of second diastereomer in solution. In analogy to
compound 4, the 13C NMR spectra showed for the cymene
moiety signals at  84.0 and 84.9 ppm (C2,6 carbon atoms, 6)
and at  86.5 and 88.7 ppm (C3,5 carbon atoms 6) (86.4, 86.9,
91.1 and 92.1 for 7). The 119Sn NMR spectra showed a singlet at
–191.2 for 6 and a doublet at -198.5 for 7 (2J(119Sn, 31P) =
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10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
Solid state structures
The molecular structures of the complexes 4 – 7 and 9 were
determined by X-ray diffraction analysis. Single crystals of
4∙2CHCl3, 5∙CH2Cl2, 6, 7∙CH2Cl2 and 9∙1.5 CH2Cl2, suitable for X-
ray analysis, were obtained by a slow solvent evaporation from
saturated solutions of 4 – 7 and 9 in the corresponding solvents.
The molecular structures of 4∙2CHCl3 and 5∙CH2Cl2 are shown in
Figure 2, selected bond distances and bond angles are given in
Table 1 and the crystallographic parameters can be consulted in
Table S1 (see SI).
Figure 3. Pov Ray presentation of the molecular structures of 6 and 7∙CH2Cl2.
Hydrogen atoms and solvent molecules are omitted for clarity.
Table 1. Selected bonding distances [Å] and angles [°] in 4 – 7 and 9.
4∙2CHCl3
5∙CH2Cl2
6
7∙CH2Cl2
(E = P1)[a]
2.3351(7)/
2.3320(7) [a]
2.5675(3)/
2.5697(3)[a]
2.3946(7)/
2.3993(8)[a]
88.68(3)/
9∙1.5CH2Cl2
(E = Sn1)
(E = P1)
(E = Sn1)
Ru-E
Ru-SnCl3
Ru-Cl
2.6006(3)
-
2.3729(5)
-
2.5963(3)
2.5738(3)
2.4371(5)
87.04(1)
89.66(1)
76.85(1)
-
-
2.5756(7)
2.5648(7)
Figure 2. Pov Ray presentation of the molecular structures of 4∙2CHCl3 and
5∙CH2Cl2. Hydrogen atoms and solvent molecules are omitted for clarity.
2.4516(8)
2.4241(8)
82.85(2)
89.13(2)
2.4181(6)
2.3982(5)
88.93(2)
90.45(2)
2.4146(17)
Both compounds 4∙2CHCl3 and 5∙CH2Cl2 show a typical piano-
stool geometry. The geometry at the ruthenium center is
essentially octahedral with cis interligand angles in the range of
82.85(2) - 89.13(2)° in 4∙2CHCl3 and 85.56(2) - 90.45(2)° in
5∙CH2Cl2, respectively. Both chlorine atoms, mutually in cis
positions (Cl2-Ru1-Cl3 = 85.26(3)° in 4∙2CHCl3 and Cl1-Ru1-
Cl1 = 85.56(2)° in 5∙CH2Cl2) are coordinated cis to the donating
atom with Sn1-Ru1-Cl3 of 89.13(2)° and Sn1-Ru1-Cl2 of
82.85(2)° in 4∙2CHCl3 and with P1-Ru1-Cl1 = 88.93(2)° and P1-
Ru1-Cl2 = 90.45(2)° in 5∙CH2Cl2, respectively. The Ru1-Sn1
distance (2.6006(3) Å) in 4∙2CHCl3 and the Ru1-P1 distance
(2.3729(6) Å) in 5∙CH2Cl2, respectively, is essentially similar to
those found in the related stannylene[11] and phosphane-arene
ruthenium complexes.[5,6] The tin atom in 4∙2CHCl3 is four-
coordinated by N1, C1, Cl1 and Ru1 atoms and exhibits a
distorted tetrahedral environment. The C1-Sn1-Cl1 angle of
107.39(7)° differs from that found in the parent
organostannylene 1 (93.99 (12)°),[10] which may be attributed to
the coordination of the Sn1 atom to the Ru1 atom.
E-Ru-Cl
-
-
88.99(3)[a]
92.79(2)
E-Ru-
SnCl3
-
-
-
-
-
-
/93.50(2)[a]
82.54(2)/
Cl-Ru-
SnCl3
89.18(5)
82.38(5)
81.08(2)[a]
Cl3Sn-Ru-
SnCl3
-
89.33(2)
[a] two independent molecules
The ruthenium atom is a stereogenic center in both complexes 6
and 7∙CH2Cl2 due to the coordination of four different ligator
atoms and thus the complexes are isolated as racemic mixtures.
The complexes show a typical piano-stool geometry with the
ruthenium center being coordinated by the arene, chloro,
trichlorostannyl and stannylene (6) or phosphane (7∙CH2Cl2)
ligand. The octahedral geometry at the ruthenium atom is very
similar to the starting complexes 4∙2CH2Cl2 and 5∙CH2Cl2 with
cis interligand angles in the range of 76.85(1) - 89.66(1)° for 6
and 81.08(2) - 93.50(2)° for 7∙CH2Cl2. However, the Ru-E
distances are clearly affected by the insertion reaction. Thus, the
Ru1-Sn1 distance in the trichlorostannyl-substituted complex 6
(2.5963(3) Å) is slightly shorter in comparison to complex
4∙2CH2Cl2 (2.6006(3) Å)). Similarly, the Ru1-P1 distance
(2.3320(7)/2.3351(7) Å) in 7∙CH2Cl2 is shorter than in the starting
complex 5∙CH2Cl2 (2.3729(5) Å). In both complexes 6 and
The molecular structures of 6 and 7∙CH2Cl2 are shown in Figure
3, selected bond distances and bond angles are given in Table 1
and the crystallographic parameters can be consulted in Table
S1 (see SI).
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10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
7∙CH2Cl2, the Ru-SnCl3 distances (2.5738(3)
Å
in 6 and
investigate all these points in more detail, a thorough DFT
2.5675(3)/2.5697(3) Å in 7∙CH2Cl2) are somewhat shorter than
those found for other neutral arene-Ru-Sn complexes (the range
of 2.5977(3) - 2.5830(9) Å).[6]
While crystalline material suitable for X-ray analysis was not
obtained in the case of 8, the molecular structure of 9, as its
dichloromethane solvate 9∙1.5CH2Cl2, was determined by X-ray
diffraction analysis (see Figure 4). Selected interatomic
computational study was performed for 4 – 7 and 9.
Computational studies
The geometries of compounds 4-7 and 9 were fully optimized
and characterized by the vibrational frequency calculations at
the B3LYP/cc-pVDZ(-PP)[12] level of theory (Figure 5) and
subsequently an NBO analysis[13] was performed. The most
relevant geometrical parameters of the studied compounds are
listed in Table 2 along with the Wiberg bond indices (WBI)[14] and
the natural population analysis (NPA) charges.[15]
distances and angles are given in Table
1
and the
crystallographic parameters are summarized in Table S1 (see
SI).
Figure 4. Pov Ray presentation of the molecular structure of 9∙1.5CH2Cl2.
Hydrogen atoms and solvent molecules are omitted for clarity.
The molecular structure of the ionic arene ruthenium complex
9∙1.5CH2Cl2 showed the presence of the [L2SnCl]+ cation that
compensates the [Ru(6-benzene)(SnCl3)2Cl]– anion with a
typical piano-stool geometry. In the [L2SnCl]+ cation, the
geometry resembles that of the complex [L2SnCl][SnCl3]
reported by Roesky et al.[8a] The Sn(1) atom is four-coordinated
by three nitrogen atoms showing relatively strong N→Sn
interactions with distances ranging between 2.305(5) (Sn1–N1)
and 2.439(5) Å (Sn1–N3) and by one chlorine atom (Sn1–Cl1
2.416(2) Å). The ruthenium atom is coordinated by the arene,
chloro and two trichlorostannyl ligands. Both Ru-SnCl3 distances
(2.5648(7) and 2.5756(7) Å) fall into the range found for the
anionic arene-Ru trichlorostannyl complexes (range of 2.546(2) -
2.5673(4) Å)[6b] and are also comparable to those found in the
neutral complexes 6 and 7∙CH2Cl2.
Figure 5. B3LYP/cc-pVDZ(-PP) optimized geometries of compounds 4-7 and
9 (Hydrogen atoms were omitted for clarity) along with selected distances (in
Å).
The WBIRu-E for the Ru-Sn and Ru-P interaction, respectively, is
predicted to be around 0.7 in the compounds 4-7, pointing to a
significant degree of covalency of the Ru-E bond. Similar WBIRu-
Thus, a set of the arene trichlorostannyl ruthenium complexes 6
– 9 allows for the investigation of the strength of the Ru-SnCl3
interaction. While the trimetallic arene ruthenium complexes 6
and 7 are neutral, the complexes 8 and 9 contain an anionic
[Ru(6-arene)(SnCl3)2Cl]– moiety. Therefore, the lability of the
Ru-SnCl3 bond with respect to the charge of the ruthenium
complex can be evaluated. Moreover, a comparison of the
complexes 4 and 5 with the related arene trichlorostannyl
ruthenium complexes 6 and 7 can reveal the influence of the
SnCl3 group on the Ru-E interaction (E = Sn, P). In order to
values were found for the interaction of the Ru atom with the
Sn
SnCl3 fragment in the compounds 6 and 7, suggesting a similar
strength and nature of both Ru-E and Ru-Sn interactions. The
calculated NPA charges revealed that the Ru-E bonds are highly
polarized in the complexes 4 and 5, with charges on the
ruthenium atoms of -0.55e and -0.34e, respectively.
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10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
Table 2. Relevant bond distances (r, Å), Wiberg bond indices (W) and NPA
atomic charges (q, e) for compounds 4-7 and 9.
Despite the anionic character of 9, the structural parameters of
the anionic part of the ionic arene ruthenium complex 9,
containing two trichlorostannyl ligands, are very similar to those
found for the trimetallic neutral complex 6 (Figure 5, Table 2).
Consequently, the NBO analysis of 9, showing two equivalent
(Ru-Sn) bonds, resulted in similar values of the NBO
populations and energies compared with values obtained for 6
(Figure 7).
4
(E=Sn)
2.668
5
(E=P)
2.449
6
(E=Sn)
2.668
7
(E=P)
2.416
9
rRu-E
-
2.657/2.668
-
[a]
rRu-Sn
-
-
2.668
0.75
2.671
0.76
WBIRu-E
0.73
0.75
[a]
WBIRu-Sn
-
-0.55
1.65
-
-
-0.34
1.45
-
0.71
-1.02
1.65
1.51
0.71
-0.78
1.45
1.52
0.73/0.72
-1.02
qRu
qE
-
[a]
qSn
1.53/1.53
[a]Sn atom of the SnCl3 fragment
The insertion of the SnCl2 into the Ru-Cl bond increases the
charge on the ruthenium atom to -1.02e and -0.78e in 6 and 7,
respectively. Consequently, this leads to a further polarization of
the Ru-E bonds in 6 and 7. Furthermore, the natural bond
orbitals analysis (NBO) of 4 and 5 showed the presence of a
(Ru-E) bond, which has a significantly higher occupancy and
lower orbital energy for the Ru-P bond in 5 (Figure 6). On the
other hand, upon insertion of the SnCl2 into the Ru-Cl bond, a
notable increase in occupancy and decrease in orbital energy
were found for the Ru-Sn bond in 6, while only slight changes
were revealed in the case of 7. Finally, the NBO analyses of 6
and 7 indicate that the (Ru-Sn) bond between the ruthenium
atom and the SnCl3 moiety is very similar in both compounds
(Figure 6).
Figure 7. Relevant NBOs (isosurface value: 0.03 a.u.) showing (Ru-Sn)
bonds in 9 (Hydrogen atoms were omitted for clarity). NBO populations and
energies are also displayed.
The influence of the trichlorostannyl ligand on the Ru-E
interaction in the complexes 4-7 can be further evaluated with a
distortion/interaction analysis. This analysis is a fragment-based
approach in which the total energy of the complex (Etot) is
decomposed into two terms: the energy associated to distorting
the fragments from their initial equilibrium structures (Edist) and
the interaction energy between those fragments (Eint):
DE = DEdist +DE
tot
int
The fragments were selected as the C,N-chelated stannylene
(L1SnCl) and amidophosphane (L3PPh2) ligands, respectively,
and the arene ruthenium moiety (ArRu). The results are
collected in Table 5. The Edist refers to the distortion energy
associated to either the stannylene or the phosphane ligand
(L1SnCl/L3PPh2) and Eint is the interaction energy computed as
follows:
DE = E
- EArRu - E 1
L SnCl/L3PPh2
1
ArRu(L SnCl/L3PPh2 )
int
Table 3. B3LYP/cc-pVDZ(-PP) distortion (Edist in kcal mol-1) and interaction
(Eint in kcal mol-1) energies computed for compounds 4-7.
ΔEtot
-30.9
-38.0
-39.5
-43.8
ΔEdist (L1SnCl/ L3PPh2)
ΔEint (ArRu-fragment)
4
5
6
7
1.7
1.5
1.6
2.0
-32.5
-39.5
-41.2
-45.8
Figure 6. Relevant NBOs (isosurface value: 0.03 a.u.) showing (Ru-E) and
(Ru-Sn) bonds in 4-7 (hydrogen atoms are omitted for clarity). NBO
populations and energies are also displayed.
This article is protected by copyright. All rights reserved.

10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
Low values of Edist for compounds 4-7, varying between 1.5
and 2.0 kcal mol–1, suggest that a very small energy is required
for the geometrical distortion of both stannylene and phosphane
ligands. However, the Eint values ranging from –32.5 to –45.8
kcal mol–1 proved that the particular E-Ru interactions between
the arene ruthenium fragment and the stannylene or phosphane
ligands are very stabilizing. In line with the NBO analysis, the P-
Ru interaction energy in 5 is about 7 kcal mol–1 more stabilizing
than the Sn-Ru interaction in 4. Furthermore, the interaction
energy in the ruthenium trichlorostannyl complexes 6 and 7
decreases to –41.2 and –43.8 kcal mol–1 (cf. –32.5 and –39.5
kcal mol-1 for 4 and 5), respectively, proving thus the stabilizing
effect of the SnCl3 ligand on the strength of Ru-E interaction
resulting from the increased negative charge on the ruthenium
atom.
Experimental Section
General Methods. The starting compounds 1 - 3 and 5 were prepared
according to the literature.[8-10] All reactions were carried out under argon,
using standard Schlenk techniques. The starting complexes [(6-
benzene)RuCl]2(-Cl)2 and [(6-cymene)RuCl]2(-Cl)2 and SnCl2 were
purchased from Sigma Aldrich. Solvents were dried by standard methods,
distilled prior to use. The 1H, 13C, 31P, and 119Sn NMR spectra were
recorded at ambient temperature with a Bruker Avance 500 spectrometer.
The chemical shifts  are given in ppm and referenced as follows:1H:
residual internal CHCl3( = 7.27 ppm);13C: internal CDCl3 ( = 77.3 ppm);
31P: external H3PO4( = 0.00 ppm); 119Sn: external SnMe4 ( = 0.00 ppm).
Synthesis of [Ru(6-cymene)(L1SnCl)Cl2] (4). A THF (15 ml) solution of
1 (0.37 g, 0.86 mmol) with [(6-cymene)RuCl]2(-Cl)2 (0.26 g, 0.43 mmol)
was stirred for 2 h. The resulting solution was evaporated to dryness and
the solid residue was washed with toluene/hexane. The insoluble red
solid was characterized as 4 (0.54 g, 85%). M.p. 218-219 °C. 1H NMR
(CDCl3, 500.13 MHz):  = 1.12 (t, 3H, CH3(Et), 3J(1H,1H) = 7.2 Hz), 1.19
(t, 3H, CH3(Et), 3J(1H,1H) = 7.2 Hz), 1.25 (d, 6H, CH3(iPr,cymene),
3J(1H,1H) = 7.8 Hz), 1.26 (s, 9H, tBu), 1.51 (s, 9H, tBu), 2.37 (s, 3H,
CH3(cymene)), 2.96 (sept. 1H, CH(iPr,cymene), 3J(1H,1H) = 7.8 Hz), 3.03
(m, 1H, CH2(Et)), 3.19 (m, 1H, CH2(Et)), 3.53 (m, 1H, CH2(Et)), 3.72 (m,
1H, CH2(Et)), 4.04 and 4.18 (AX system, 2H, CH2N), 5.52 and 5.67 (AX
system, 2H, ArH(cymene)), 5.57 and 5.71 (AX system, 2H, ArH(cymene)),
6.99 (s, 1H, ArH), 7.39 (s, 1H, ArH) ppm. 13C{1H} NMR (CDCl3, 125.77
Conclusions
A set of neutral and ionic ruthenium arene trichlorostannyl
complexes was prepared. While the stannylene L1SnCl (1)
reacts with [(6-cymene)RuCl]2(-Cl)2 as a neutral donor ligand
yielding the complex [Ru(6-cymene)(L1SnCl)Cl2] (4) , the ionic
compound [L2SnCl][SnCl3] (2) provided the ionic product
[L2SnCl][Ru(6-cymene)(SnCl3)2Cl] (8). The insertion reaction of
SnCl2 with 4 yielded the neutral trimetallic ruthenium complex
[Ru(6-cymene)(L1SnCl)(SnCl3)Cl] (6). Analogous complexes
MHz):
 = 7.6, 12.3 (CH3(Et)), 18.3 (CH3(cymene)), 22.4, 22.8
(CH3(iPr,cymene)), 30.5 (CH(iPr,cymene)), 31.2 (CH3(tBu)), 32.8
(CH3(tBu)), 34.7 (C(tBu)), 36.9 (C(tBu)), 46.9, 47.8 (CH2(Et)), 59.4
(CH2N), 82.5, 84.1, 84.4, 84.8, 96.8, 104.1 (Ar-C(cymene)), 121.3, 124.1,
140.9, 142.9, 152.3, 157.6 (Ar-C) ppm. 119Sn{1H} NMR (CDCl3, 186.36
MHz):  = -14.6 ppm. C29H46Cl3NRuSn (734.82): calcd. C 47.40, H 6.31,
found C 46.95, H 6.25.
[Ru(6-cymene)(L3PPh2)Cl2]
(5)
and
[Ru(6-
cymene)(L3PPh2)(SnCl3)Cl] (7) containing the phosphane ligand
L3PPh2 (3) were prepared and therefore the donor-acceptor
interaction of the tin(II) and phosphorus atoms with the
ruthenium atoms was studied. The influence of the
trichlorostannyl ligand on the Ru-E interaction in the complexes
4 - 7 was evaluated by structural characterization as well as by
DFT calculations. The calculated NPA charges revealed highly
polarized Ru-E bonds in both complexes 4 and 5 with a charge
on the ruthenium atom of –0.55e in 4 and –0.34e in the
phosphane-containing analogue 5. Moreover, the insertion of
SnCl2 into the Ru-Cl bond increases the negative charge on the
ruthenium atom in 6 and 7 to –1.02e and –0.78e, respectively.
The influence of the trichlorostannyl ligand on the Ru-E
interaction in the complexes 4 - 7 was further evaluated with a
distortion/interaction analysis. The Eint values were calculated
for compounds 4 and 5 and showed that the Ru–P interaction
energy in 5 is about 7 kcal mol–1 more stabilizing than the Ru–
Sn interaction in 4. Furthermore, the interaction energy in the
ruthenium trichlorostannyl complexes 6 and 7 decreases to
–41.2 and –45.8 kcal mol–1, respectively. It is evident that the
insertion of SnCl2 resulted in an increase of the negative charge
on the ruthenium center and as a consequence, the Ru-E (E =
Sn, P) interaction is stronger in 6 and 7. The stabilization effect
of the [SnCl3]– moiety is stronger for the stannylene–Ru
interaction in complexes 4 and 6, where the Eint value rises
from –32.5 to –41.2 kcal∙mol–1.
Synthesis of [Ru(6-cymene)(L1SnCl)(SnCl3)Cl] (6).
A THF (15 ml) solution of 4 (0.48 g, 0.65 mmol) with SnCl2 (0.13 g,
0.65 mmol) was stirred for 24 h at room temperature. The resulting
solution was evaporated to dryness and the solid residue was washed
with toluene/hexane to provide an orange solid, which was re-crystalized
from CH2Cl2 solution to give 6 as suitable material for X-ray diffraction
analysis (0.54 g, 85%). M.p. 225-227 °C. H NMR (CDCl3, 500.13 MHz):

= = 7.2 Hz), 1.28 (d, 6H,
1.09 (t, 3H, CH3(Et), 3J(1H,1H)
CH3(iPr,cymene), 3J(1H,1H) = 7.6 Hz), 1.29 (s, 9H, tBu), 1.47 (t, 3H,
CH3(Et), 3J(1H,1H) = 7.2 Hz), 1.50 (s, 9H, tBu), 2.17 (s, 3H, CH3(cymene)),
2.84 (sept, 1H, CH (iPr,cymene), 3J(1H,1H) = 7.6 Hz), 3.00 (m, 1H,
CH2(Et)), 3.08 (m, 1H, CH2(Et)), 3.45 (m, 1H, CH2(Et)), 3.78 (m, 1H,
CH2(Et)), 3.89 and 4.25 (AX system, 2H, CH2N), 5.80 and 6.07 (AX
system, 2H, ArH(cymene)), 5.88 and 6.12 (AX system, 2H, ArH(cymene)),
7.03 (s, 1H, (ArH)), 7.48 (s, 1H, (ArH)) ppm. 13C{1H} NMR (CDCl3, 125.77
MHz):
 = 6.5, 12.7 (CH3(Et)), 18,6 (CH3(cymene)), 22.0, 22.6
(CH3(iPr,cymene)), 30.5 (CH(iPr,cymene)), 31.2 (CH3(tBu)), 32.6
(CH3(tBu)), 33.3 (C(tBu)), 34.8 (C(tBu)), 37.6 (CH2(Et)), 44.6 (CH2(Et)),
59.2 (CH2N), 84.0, 84.9, 86.5, 88.7, 97.0, 114.0 (Ar-C(cymene)), 121.8,
125.0, 139.3, 145.2, 153.2, 157.2, 158.1 (Ar-C) ppm. 119Sn{1H} NMR
(CDCl3, 186.36 MHz):
 =
-191.2 (SnCl3), 110.1 (L1SnCl) ppm.
C29H46Cl5NRuSn2 (924.44): calcd. C 37.68, H 5.02; found C 37.47, H
4.98.
Synthesis of [Ru(η6-cymene)(L3PPh2)(SnCl3)(Cl)] (7).
A THF (15 ml) solution of 5 (0.87 g, 1.30 mmol) with SnCl2 (0.25 g,
1.30 mmol) was stirred for 24h at room temperature. The resulting
This article is protected by copyright. All rights reserved.

10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
solution was evaporated to dryness and the solid residue was washed
with toluene/hexane to provide orange solid, which was re-crystalized
from CH2Cl2 / hexane solution at +4°C to give 7 (0.90 g, 81%). M.p. 213-
215 °C. 1H NMR (CDCl3, 500.13 MHz):  = 0.49 (d, 6H, CH3(iPr),
3J(1H,1H) = 6.5 Hz), 0.56 (d, 6H, CH3(iPr), 3J(1H,1H) = 6.5 Hz), 1.13 (s, 3H,
CH3(cymene)), 1.18 (d, 3H, CH3(iPr,cymene), 3J(1H,1H) = 7.0 Hz), 1.30 (d,
(for 5, 6, and 9) or chloroform (for 4) solutions. Crystals were mounted on
a glass fiber with an inert viscous oil and measured on a KappaCCD
diffractometer with a CCD area detector by monochromatized MoKα
radiation ( = 0.71073 Å) at 150(2) K (4∙2CHCl3, 5∙CH2Cl2, 6, 7∙CH2Cl2).
Intensity data for 9∙1.5CH2Cl2 were collected on an XcaliburS CCD
diffractometer (Oxford Diffraction) using Mo-Kα radiation at 110 K. The
details pertaining to the data collection and refinement for crystals are
given in Table S1 (see Supporting Information). Data reductions were
performed with DENZO-SMN (4∙2CHCl3, 5∙CH2Cl2, 6, 7∙CH2Cl2).[16] The
absorption was corrected by integration methods (4∙2CHCl3, 5∙CH2Cl2, 6,
7∙CH2Cl2).[17] Structures were solved by direct methods (Sir92)[18]
(4∙2CHCl3, 5∙CH2Cl2, 6, 7∙CH2Cl2) and SHELXS-97[19] (9∙1.5CH2Cl2),
respectively, and refined by full matrix least-square based on F2
(SHELXL97 and SHELXL2014/6, respectively).[20] Hydrogen atoms were
3H, CH3(iPr,cymene), 3J(1H,1H)
=
7.0 Hz), 2.55 (sept, 1H,
CH(iPr,cymene), 3J(1H,1H) = 7.0 Hz), 3.09 (sept, 1H, CH(iPr), 3J(1H,1H) =
6.5 Hz), 4.68 (d, 1H, NH, 2J(31P,1H) = 11.5 Hz), 5.24 and 5.79 (AX
system, 2H, ArH(cymene)), 5.44 and 6.09 (AX system, 2H, ArH(cymene)),
6.73 (d, 2H, ArH, 3J(1H,1H) = 7.5 Hz), 6.94 (t, 1H, ArH, 3J(1H,1H) = 7.5
Hz), 7.33-7.51 (m, 8H, ArH), 7.78 (m, 2H, ArH) ppm. 13C{1H} NMR
(CDCl3, 125.77 MHz):
 = 16.2, 22.3 (CH3(iPr,cymene)), 23,2
(CH3(cymene)), 23.9 (CH(iPr)), 28.1 (CH3(iPr)), 30.5 (CH(iPr,cymene)),
86.4, 86.9, 91.1, 92.1, 97.8, 120.7 (Ar-C(cymene)), 123.2, 126.9, 127.3,
128.1, 130.1, 131.0, 133.3, 134.7, 135.1, 137.1, 147.8, 147.9 (Ar-C) ppm.
31P{1H} NMR (CDCl3, 202.40 MHz):  = 79.4 ppm. 119Sn{1H} NMR (CDCl3,
mostly localized on
a difference Fourier map, however to ensure
uniformity of the treatment of the crystal, all hydrogen atoms were
recalculated into idealized positions (riding model) and assigned
temperature factors Hiso(H) = 1.2 Ueq (pivot atom) or of 1.5Ueq for the
methyl moiety with C-H = 0.98, 0.97, and 0.93 Å for methyl, methylene
and hydrogen atoms in aromatic rings, respectively. The structure of
compound 5 contains a disorder of one of the chlorine atoms in the
dichloromethane molecule, the chlorine atom was split into two positions
with an occupancy of about 1:1. This disorder has been treated by
standard SHELXL software instructions.[20] CCDC-1511592 (4·2CHCl3),
CCDC-1511593 (5·CH2Cl2), CCDC-1511594 (6), CCDC-1511595
(7·CH2Cl2) and CCDC-1518855 (9·1.5CH2Cl2) contain the supplementary
crystallographic data for this paper. This data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
186.36 MHz):

=
-198.5 (SnCl3, 2J(119Sn,31P)
=
665 Hz).
C34H42Cl4NPRuSn (857.27): calcd. C 47.64, H 4.94; found C 47.28, H
4.75.
Synthesis of [L2SnCl] [Ru(6-cymene)(SnCl3)2Cl] (8).
A CH2Cl2 (30 ml) solution of 3 (0.60 g, 0.7 mmol) was added with stirring
to [(6-cymene)RuCl]2(-Cl)2 (0.1 g, 0.175 mmol) at room temperature.
The reaction mixture was further stirred for additional 24 h. The solution
was filtered and the filtrate was concentrated to
a volume of
approximately 10 ml. Storing it overnight at 4°C gave the orange solid of
8 (0.43 g, 91%). M.p. 208.3 °C with dec.; 1H NMR (CDCl3, 500.13 MHz):
 = 1.16 (d, 12H, CH(CH3)2, 3J(1H,1H) = 8.0 Hz), 1.23 (d, 12H, CH(CH3)2,
3J(1H,1H) = 8.0 Hz), 1.25 (d, 6H, iPr, cymene, 3J(1H,1H) = 6.0 Hz), 2.15 (s,
3H, iPr, cymene), 2.64 (s, 6H, (CH3)C=N), 2.75 (sept, 4H, CH(CH3)2,
3J(1H,1H) = 8.0 Hz), 2.86 (sept, 1H, iPr, cymene, 3J(1H,1H) = 6.0 Hz), 5.77
and 5.88 (dd, 4H, ArH(cymene)), 7.30-7.39 (m, 6H, ArH), 8.61 (d, 2H,
ArH, 3J(1H,1H) = 8.5 Hz), 8.93 (t, 1H, ArH, 3J(1H,1H) = 8.5 Hz) ppm.
13C{1H} NMR (CDCl3, 125.77 MHz):  = 18.8 (CH3(iPr), cymene), 19.6
((CH3)C=N), 22.8 (CH3, cymene), 24.8 (CH3(iPr)), 25.2 (CH3(iPr)), 28.4
(CH(iPr)), 29.3 (CH(iPr)), 30.9 (CH(iPr), cymene), 84.9, 86.5, 102.1,
108.9, 124.9, 125.0, 128.2, 130.8, 136.8, 139.5, 140.4, 147.0, 149.6,
169.3 (C=N) ppm. 119Sn{1H} NMR (CDCl3, 186.36 MHz):  = -160.2
(SnCl3), -423.1([L2SnCl]+) ppm. C43H57N3Cl8RuSn3 (1356.7): calcd. C
38.07, H 4.23; found C 38.25, H 4.35.
Computational details. All calculations were carried out using Density
Functional Theory (DFT) as implemented in the Gaussian09 quantum
chemistry program.[21] Geometry optimizations were carried out at the
B3LYP/cc-pVDZ level of theory (for heavier atoms - Ru and Sn - the cc-
pVDZ-PP basis set including small-core relativistic pseudopotentials that
account also for relativistic effects was used).[12] The electronic energies
were re-evaluated by additional single point calculations on each of all
optimized geometries using the triple-ζ-quality cc-pVTZ(-PP) basis set.
Analytical vibrational frequencies within the harmonic approximation were
computed with the cc-pVDZ basis set to confirm proper convergence to
well-defined minima or saddle points on the potential energy surface.
Subsequent NBO analysis13 and calculation of Wiberg bond indices[14]
were performed at the B3LYP6/cc-pVDZ(-PP) level.
Synthesis of [L2SnCl] [Ru(6-benzene)(SnCl3)2Cl] (9).
A CH2Cl2 (30 ml) solution of 3 (0.60 g, 0.7 mmol) was added with stirring
to [(6-benzene)RuCl]2(-Cl)2 (0.09 g, 0.175 mmol) at room temperature.
The reaction mixture was further stirred for additional 24 h. The solution
was concentrated to a volume of approximately 10 ml. Storing it at room
temperature for three days provided the orange solid of 9∙1.5CH2Cl2 (0.8
g, 86%). M.p. 221.8°C with decomp.; 1H NMR (CDCl3, 500.13 MHz):  =
1.14 (d, 12H, CH(CH3)2, 3J(1H,1H) = 7.2 Hz), 1.22 (d, 12H, CH(CH3)2,
3J(1H,1H) = 7.2 Hz), 2.62 (s, 6H, (CH3)C=N), 2.74 (bs, 4H, CH(CH3)2),
5.83 (s, 6H, C6H6), 7.15 – 7.31 (m, 6H, ArH), 8.61 (d, 2H, ArH, 3J(1H,1H)
= 7.8 Hz), 8.91 (t, 1H, ArH, 3J(1H,1H) = 7.8 Hz) ppm. 13C{1H} NMR (CDCl3,
125.77 MHz): 19.6 (CH3(iPr)), 22.8 ((CH3)C=N), 24.9 (CH(iPr)), 86.7,
125.3, 128.2, 129.0, 130.7, 136.7, 140.4, 149.6, 169.3 ppm. 119Sn{1H}
NMR (CDCl3, 186.36 MHz): = -159.1 (SnCl3), -423.0 ([L2SnCl]+) ppm.
ESI/MS: positive part m/z 636.2 [L2SnCl]+; negative part m/z 666.5
Acknowledgements
The authors wish to thank TACR (project no. TH02010197) and
the Ministry of Industry and Trade of the Czech Republic (project
FV-10240) for the financial support. J.T. and F.D.P. wish to
acknowledge the Free University of Brussels (VUB) for the
Strategic Research Program. M.B. is grateful to the German
Academic Exchange Board (DAAD) for a scholarship.
Keywords: tin • ruthenium • NMR • DFT calculations•
complexes
[Ru(6-benzene)(SnCl3)2Cl]. C40.5H52N3Cl11RuSn3 (1427.94): calcd.
C
34.03, H 3.93; found C 35.09, H 3.80.
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This article is protected by copyright. All rights reserved.

10.1002/ejic.201700098
European Journal of Inorganic Chemistry
FULL PAPER
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This article is protected by copyright. All rights reserved.

10.1002/ejic.201700098
European Journal of Inorganic Chemistry
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FULL PAPER
A set of Sn(II)-Ru arene trichlorostannyl
complexes was prepared. As a result of
different properties of tin(II) donor
ligands, either neutral or ionic trimetallic
arene ruthenium complexes were
isolated. Structurally related phosphane
compounds were also prepared and the
E – Ru donor-acceptor interactions (E =
Sn, P) were studied by DFT calculations.
Tin-ruthenium complexes
Miroslav Novák, Marek Bouška, Libor
Dostál, Michael Lutter, Klaus Jurkschat,
Jan Turek,* Frank De Proft, Zdeňka
Růžičková, Roman Jambor*
Page No. – Page No.
Title
Moreover,
the influence
of the
trichlorostannyl ligand on the Ru-E
interaction was evaluated with
distortion/interaction analysis
a
This article is protected by copyright. All rights reserved.