Stabilization of an intramolecularly coordinated stannylidenium cation

Article abstract of DOI:10.1002/zaac.201200064

The treatment of trans-{[2, 6-(Me₂NCH₂) ₂C₆H₃]SnI}₂PtI₂ with Na(pyt) (pyt = 2-mercaptopyridine) yielded the unprecedented complex {{[2, 6-(Me₂NCH₂)₂C₆H₃]Sn} Pt(μ-pyt)₂I} (1), where a Sn←N coordinated stannylidenium (LSn^II)⁺ fragment donates a to a [Pt^II(pyt) ₂I]^- anion. Compound 1 was characterized by NMR spectroscopy and molecular structure was determined by X-ray diffraction analysis. The bonding situation in 1 was analyzed by DFT studies. Copyright

Full text of DOI:10.1002/zaac.201200064

SHORT COMMUNICATION
DOI: 10.1002/zaac.201200064
Stabilization of an Intramolecularly Coordinated Stannylidenium Cation
Jana Martincová,[a] Libor Dostál,[a] Alesˇ Ru˚zˇicˇka,[a] Sonja Herres-Pawlis,*[b] and
Roman Jambor*[a]
Dedicated to Professor Klaus Jurkschat on the Occasion of His 60th Birthday
Keywords: Chelating ligand; Tin; Platinum; NMR spectroscopy; Metal bonding
Abstract. The treatment of trans-{[2,6-(Me2NCH2)2C6H3]SnI}2PtI2 [PtII(pyt)2I]– anion. Compound 1 was characterized by NMR spec-
with Na(pyt) (pyt = 2-mercaptopyridine) yielded the unprecedented troscopy and molecular structure was determined by X-ray diffraction
complex {{[2,6-(Me2NCH2)2C6H3]Sn}Pt(μ-pyt)2I} (1), where
a
analysis. The bonding situation in 1 was analyzed by DFT studies.
SnǟN coordinated stannylidenium (LSnII)+ fragment donates a to a
moiety is stabilized by intramolecular coordination of the pyr-
idyl groups[8] (Scheme 1A) and we have also reported the iso-
lation of [({2,6-(Me2NCH2)2C6H3}Sn)(μ-pyt)2PtCl], where 2-
mercaptopyridine was used as the bridge for a SnII cation and
Introduction
The chemistry of transition metal (TM) complexes contain-
ing various SnII-based ligands is an active research area since
they seem to be catalytic reagents for a variety of reactions,
depending on the type of transition metal involved.[1] Tin di-
chloride, as the simplest example of SnII-based ligands, is an
important co-catalyst in various group 10 metal-catalyzed reac-
tions such as hydroformylation,[2] hydrogenation,[3] isomeriza-
tion,[4] or hydrogen-mediated reductive couplings.[5] These
TM-SnII complexes are usually prepared by reactions of the
TM-Cl complexes with stannylene SnR2 (where R is an organic
or inorganic substituent), via the insertion of a SnR2 into a
TM–Cl bond to yield complexes of the general formula [TM–
SnR2Cl] having weakly coordinated [SnR2Cl]– anions.[6] This
weak coordination of [SnR2Cl]– anion and/or its trans-labiliz-
ing effect has been used to explain the importance of stannyl-
enes SnR2 as co-catalysts. The exact role of the SnR2 frag-
ments is still unclear[7] and studies dealing with the synthesis
and properties of TM complexes that contain various SnII-
based ligands are of interest for this reason. Recently, Deelman
et al. reported that the reaction of SnCl2 with [M(X)(Cl)(2-
PyPPh2)2] precursors (X = Cl, Me) yielded cationic complexes
[M(X)(SnCl2(2-PyPPh2)2)]+, in which a dichlorostannylene
a
PtII anion (hereafter, pyt
(Scheme 1B).[9]
=
2-mercaptopyridine)
Scheme 1. Tin-platinum complexes stabilized by intramolecular coor-
dination.
Herein, we present the synthesis of [({2,6-(Me2NCH2)
2C6H3}Sn)(μ-pyt)2PtI] (1), an iodide analogue of the latter
compound. Complex 1 was characterized by NMR spec-
troscopy, elemental analysis and the molecular structure was
determined by single-crystal X-ray diffraction analysis.
Furthermore, theoretical calculations using density functional
theory (DFT) were performed on compound 1.
* Prof. Dr. S. Herres-Pawlis
E-Mail: sonja.herres-pawlis@cup.uni-muenchen.de
* Dr. R. Jambor
E-Mail: roman.jambor@upce.cz
[a] Department of General and Inorganic Chemistry
University of Pardubice
Results and Discussion
The reaction of trans-{[2,6-(Me2NCH2)2C6H3]SnI}2PtI2
with 3 equiv. of Na(pyt) yielded the complexes {2,6-
(Me2NCH2)2C6H3}Sn(pyt) and [({2,6-(Me2NCH2)2C6H3}Sn)-
(μ-pyt)2PtI] (1) (Scheme 2).
While the by-product {2,6-(Me2NCH2)2C6H3}Sn(pyt) was
isolated and characterized according to previous NMR spectro-
scopic data,[9] the sparingly soluble compound 1 represents a
Studentská 95
53210, Pardubice, Czech Republic
[b] Department Chemie
Ludwig-Maximilians-Universität München
Butenandtstr. 5
81377 München, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200064 or from the au-
thor.
Z. Anorg. Allg. Chem. 2012, 638, (᭿), 1–5
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

S. Herres-Pawlis, R. Jambor et al.
SHORT COMMUNICATION
Scheme 2. Synthesis of complex 1.
1
new SnIIǞPtII complex that was characterized by H NMR Sn(1) and the I(1) atoms. The Sn(1) and I(1), and S(1) and
spectroscopy and single-crystal X-ray diffraction analysis. S(1A) atoms are mutually trans with Sn(1)–Pt(1)–I(1) and
The 1H NMR spectrum revealed a singlet of the CH2N protons
S(1)–Pt(1)–S(1a) bond angles of 180.0° and 173.80(6)°,
at δ = 3.69 ppm, a singlet of the NCH3 protons at δ = 2.19 ppm
of the N,C,N-chelating ligand. The signals at 6.58, 6.75, 7.49,
and 7.87 ppm confirmed the presence of the pyt polar group.
Other NMR spectroscopic data could not be obtained due to
the poor solubility of 1 in organic solvents. The molecular
structure of compound 1 was, however, determined by single-
crystal X-ray diffraction analysis and is depicted in Figure 1.
Selected geometrical parameters are given in the Figure cap-
tion.
respectively. The distances of the Pt(1)–I(1) [2.6757(5) Å],
Pt(1)–S(1) and Pt(1)–S(1a) [2.2748(17) Å] bonds correspond
to covalent Pt–I and Pt–S bonds found in other PtII complexes
containing pyridine-2-thionate ligands.[11] The Sn(1)–Pt(1)
bond length of 2.4712(5) Å in 1 is comparable to that found
in [({2,6-(Me2NCH2)2C6H3}Sn)(μ-pyt)2PtCl] [2.4661(6) Å],[9]
but is significantly shorter than that found in the cationic
square-planar platinum complex trans-[Pt(Me)(SnCl2)(2-
PyPPh2)2]+[BF4]– [2.5166(6) Å].[8] In relation to the theoreti-
cal single Sn–Pt bond estimated to 2.63 Å by Pyykkö and Ats-
umi,[12] the value of 2.4712(5) Å appears rather short. How-
ever, the comparison with the theoretical Sn–Pt double bond
(2.42 Å)[12] reveals that the present Sn(1)–Pt(1) bond length
is too long for a double bond. The octahedral coordination
arrangement of the Sn(1) atom consists of two nitrogen atoms
N(1), N(1a) of the ligand L, two nitrogen atoms N(2), N(2a)
of pyt groups and the C(1) and Pt(1) atoms all being mutually
in trans positions as defined from N(1)–Sn(1)–N(1a) =
150.12(2)°, N(2)–Sn(1)–N(2a) = 174.92(19)°, and C(1)–
Sn(1)–Pt(1) = 180.0°. The most interesting feature is that the
values of all Sn–N bond lengths [range of 2.414(4)–
2.437(5) Å] indicate the presence of SnǟN donor-acceptor in-
teractions, leaving thus the C(1)–Sn(1) bond [2.127(8) Å] as
the only covalent bond of the central SnII atom. The latter fact
together with the presence of three covalent bonds at PtII sug-
gest the presence of a SnǟN coordinated stannylidenium
(LSnII)+ fragment donating to a [Pt(pyt)2I]– anion. Apparently,
an additional intramolecular donation of the nitrogen lone pairs
of the pyt ligands to the tin atom, leading to a hexacoordinate
octahedral arrangement, seems to stabilize the stannylidenium-
type coordination of the (LSnII)+ moiety on the central PtII
atom.
Figure 1. Molecular structure of 1 together with selected bond
lengths /Å and angles /°: The thermal ellipsoids are drawn with 50%
probability. Hydrogen atoms and one CH2Cl2 molecule are omitted for
clarity. Selected bond lengths /Å and angles /°: Sn(1)–Pt(1) 2.4712(5),
Pt(1)–I(1) 2.6757(5), Pt(1)–S(1a) 2.2748(17), Pt(1)–S(1) 2.2748(17),
Sn(1)–N(1) 2.437(5), Sn(1)–N(2) 2.414(4), Sn(1)–C(1) 2.127(8);
Sn(1)–Pt(1)–I(1) 180.00, S(1)–Pt(1)–S(1a) 173.80(6), S(1)–Pt(1)–I(1)
86.90(3), Sn(1)–Pt(1)–S(1) 93.10(3).
The structure of 1 consists of a four-coordinate platinum
atom with a square-planar configuration and a six-coordinate
SnII atom with a distorted octahedral arrangement. Complex 1
exhibits a unique I–PtII–SnII–C bond bridged by two head-to-
head coordinating pyt ligands. The closest structural analogy
is the cationic square-planar platinum complex trans-[Pt(Me)
(SnCl2)(2-PyPPh2)2]+[BF4]– in which the Pt–SnCl2 bond is
bridged by two head-to-head coordinated 2-PyPPh2 ligands[8]
and the neutral complex [PdSn(μ-mt)4Cl2] with the PdIIǞSnIV
dative bond bridged by four methimazolyl (mt) groups.[10]
The square planar configuration of the Pt(1) atom is formed
To gain theoretical insight into the bonding situation in 1,
DFT calculations were performed. The geometry optimization
using the BP86/def2-TZVP methodology reproduces the ar-
rangement of the solid state very well. Use of fully relativistic
effective core potentials yielded no significant difference in
comparison to non-relativistic effective core potentials (see
Supporting Information). The bonding situation can be inter-
preted as a SnǟN coordinated stannylidenium (LSnII)+ frag-
ment donating to a [PtII(pyt)2Cl]– anion. The Sn–Pt binding
by the S(1) and S(1a) atoms of the pyt groups, and by the orbital is depicted at Figure 2.
2
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–5

Stabilization of an Intramolecularly Coordinated Stannylidenium Cation
Table 1. Second order perturbation analysis. a) BD: binding electron
pair. b) LP: lone pair.
Charge Transfer
Energy /kcal·mol–1
LPa)(Pt)Ǟ LP*(Sn)
LP(S)Ǟ LP*(Pt)
LP(I)Ǟ LP*(Pt)
6.08
15.94
7.74
LP(py)Ǟ LP*(Sn)
LP(amine)ǞLP*(Sn)
LP(py)Ǟ LP*(Sn)
LP(amine)ǞLP*(Sn)
LP(Pt)Ǟ BDb)*(Sn–C)
LP(Pt)Ǟ BD*(Pt–Sn)
BD(Sn–C)ǞBD*(Sn–Pt)
75.03
46.88
75.03
46.88
10.05
6.73
15.47
Conclusions
The treatment of trans-{[2,6-(Me2NCH2)2C6H3]SnI}2PtI2
with Na(pyt) yielded the unprecedented complex [({2,6-
(Me2NCH2)2C6H3}Sn)(μ-pyt)2PtI] (1), where a SnǟN coordi-
nated stannylidenium (LSnII)+ fragment donates to a [PtII(pyt)2-
Cl]– anion. The bonding situation in 1 was analyzed by DFT
and showed that the nature of the Sn–Pt interaction is very
complex. The lone electron pair of SnII atom was consumed
for the formation of the tin–platinum bond and SnIIǞPtII do-
nation in this complex can be also interpreted as a SnIVǟPt0
interaction.
Figure 2. The Sn–Pt-binding orbital of complex 1.
The NBO analysis[13] revealed no lone pair at the tin atom
and the natural charge of tin atom is +1.715, while that at the
platinum atom is –0.712. These observations can be rational-
ized with the lone electron pair of the SnII atom being shared
by both atoms and consumed for the formation of a covalent
tin–platinum bond. The NBO analysis[13] showed that the na-
ture of the Sn–Pt bond is mediated by sp-hybridized orbitals
on the tin atom (one sp-hybrid for the Sn–Pt bond and one for
the Sn–C bond). The natural electron configuration of the tin
atom is 5s1.25 and 5p0.98 indicating that nearly one electron
was fully consumed for the formation of this bond and sug-
gests highly covalent character of this bond. The Wiberg bond
index of this bond amounts to 0.762. However, the formal
presence of two covalent bonds on the tin atom with the natu-
Experimental Section
General: All reactions were carried out in an argon atmosphere, using
standard Schlenk techniques. Solvents were dried by standard methods,
distilled prior to use. The starting compound trans-{[2,6-(Me2NCH2)2-
C6H3]SnI}2PtI2 was prepared according to the literature[14] and NaI
1
and H(pyt) was purchased from Sigma-Aldrich. The H NMR spectra
were recorded at ambient temperature with a Bruker Avance 500 spec-
trometer. The chemical shifts δ are given in ppm and referenced to
ral charge of about + 2 and the negative formal charge on external SiMe4 (1H).
platinum also suggests another possible interpretation of the
Synthesis of [{(2,6-(Me2NCH2)2C6H3}Sn)Pt(μ-pyt)2I] (1): A solu-
Sn–Pt bond to be a SnIVǟPt0 interaction.[10] This is in accord-
ance with the larger electronegativity of platinum in compari-
son to tin. Hence, the electrons of the covalent Sn–Pt bond
have to be counted for platinum. The nature of the Sn–Pt inter-
action can thus be described by both frontier formulae until
further measurements (such as Mössbauer spectroscopy) clar-
ify the tin oxidation state.
The highly positively charged tin atom (+ 1.715, and for-
mally + IV with this interpretation) is further stabilized by
several strong N donor interactions and an additional donor
interaction (found with second order perturbation theory) of
PtǞSn (Table 1), hence lowering the formal charge. This is in
line with the shortened Sn–Pt bond length. Moreover, the ionic
part of a SnIVǟPt0 interaction supports the decrease of the
Sn–Pt bond length. The sulfur–platinum bonds have covalent
character (75% S, 25% Pt) but they are supported by ad-
ditional donor interactions from the sulfur atoms. The whole
system is strongly delocalized, which is reflected in the donor
interactions from the lone pairs of the platinum atom into the
C–Sn bond and the Pt–Sn bond (antibonding orbitals BD*).
tion of trans-{[2,6-(Me2NCH2)2C6H3]SnI}2PtI2 (0.18 g, 0.14 mmol) in
CH2Cl2 (40 mL) was stirred with Na(pyt) (0.57 g, 0.42 mmol) in THF
(40 mL) for 24 h. The resulting mixture was filtered, evaporated to
dryness, and the solid residue was extracted with toluene (2ϫ5 mL).
The toluene fraction was evaporated and the solid residue charac-
terized as {2,6-(Me2NCH2)2C6H3}Sn(pyt) by NMR spectroscopic data,
which were consistent with those published previously.[9] The solid
residue insoluble in toluene was extracted with CH2Cl2 (2ϫ15 mL)
and organic solution was concentrated by slow evaporation of CH2Cl2
to approx. 5 mL during of what the crystalline material suitable for X-
ray structure analysis appeared. The crystalline material was separated
by decantation and washed with hexane to give complex 1 as red solid.
Yield 48 mg (40%); m.p. 245 °C (decomp.). C22H29IN4PtS2Sn
(854.32): calcd. C 30.93; H 3.42%; found: C 30.90; H 3.39%. 1H
NMR (500.13 MHz, CDCl3): δ = 7.87 (d, 2 H, pyridine), 7.49 (t, 2 H,
pyridine), 7.20 (d, 2 H, ArH), 7.03 (t, 1 H, ArH), 6.75 (d, 2 H, pyr-
idine), 6.58 (t, 2 H, pyridine), 3.69 (s, 4 H, CH2N), 2.19 (s, 12 H,
NCH3) ppm.
Crystallographic Details for Compound 1: Single crystals of 1
(orange) were obtained by slow evaporation from their respective solu-
tions in dichloromethane. Compound 1 crystallized as a solvate with
Z. Anorg. Allg. Chem. 2012, 1–5
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3

S. Herres-Pawlis, R. Jambor et al.
SHORT COMMUNICATION
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CH2Cl2 molecule. Crystals were mounted on a glass fiber with epoxy
cement and measured with a KappaCCD diffractometer with a CCD
area detector by monochromatized Mo-Kα radiation (λ = 0.71073 Å)
at 150(1) K. The details pertaining to the data collection and refine-
ment
for
crystals
are
as
follows
for
1·CH2Cl2:
C21H27IN4PtS2Sn·CH2Cl2, M.w. = 925.19, monoclinic, space group
C2/c, a = 14.3761(8), b = 14.1379(9), c = 17.0359(11) Å, α = 90°, β =
108.837(9)°, γ = 90°, Z = 4, ρ(calcd) = 1.875 Mg·m–3, μ = 6.275 mm–1,
crystal size 0.39ϫ0.31ϫ0.09 mm, crystal shape plate, θ range 1 to
25.75°, 17847 reflections collected, of which 3706 were independent
[R(int) = 0.046], [I Ͼ 2σ(I)]: R1 = 0.0394, wR2 = 0.0982.
Crystallographic data (excluding structure factors) for the structure in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
number CCDC-795541 (Fax: +44-1223-336-033; E-Mail: deposit@-
ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
Supporting Information (see footnote on the first page of this article):
Crystallographic details, CIF. file and computational details.
Acknowledgement
The authors wish to thank the Grant Agency of the Czech Republic
(project no. GAP207/10/0215) for financial support. S. H.-P. thanks
the Fonds der Chemischen Industrie for granting a Liebig fellowship
and the Bundesministerium für Bildung und Forschung (MoSGrid,
01IG09006) for financial support.
[9] J. Martincová, L. Dostál, S. Herres-Pawlis, A. Ru˚zˇicˇka, R.
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Received: February 16, 2012
Published Online: ᭿
4
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Z. Anorg. Allg. Chem. 2012, 1–5

Stabilization of an Intramolecularly Coordinated Stannylidenium Cation
J. Martincová, L. Dostál, A. Ru˚zˇicˇka, S. Herres-Pawlis,*
R. Jambor* ........................................................................ 1–5
Stabilization of an Intramolecularly Coordinated Stannyliden-
ium Cation
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