Insights into the intramolecular donor stabilisation of organostannylene palladium and platinum complexes: Syntheses, structures and DFT calculations

Article abstract of DOI:10.1002/chem.201203511

The syntheses of the transition metal complexes cis-[(4-tBu-2,6-{P(O)(OiPr) ₂}₂C₆H₂SnCl)₂MX ₂] (1, M=Pd, X=Cl; 2, M=Pd, X=Br; 3, M=Pd, X=I; 4, M=Pt, X=Cl), cis-[{2,6-(Me₂NCH₂)₂C₆H ₃SnCl}₂MX₂] (5, M=Pd, X=I; 6, M=Pt, X=Cl), trans-[{2,6-(Me₂NCH₂)₂C₆H ₃SnI}₂PtI₂] (7) and trans-[(4-tBu-2,6-{P(O) (OiPr)₂}₂ C₆H₂SnCl)PdI ₂]₂ (8) are reported. Also reported is the serendipitous formation of the unprecedented complexes trans-[(4-tBu-2,6-{P(O)(OiPr) ₂}₂C₆H₂SnCl)₂ Pt(SnCl₃)₂] (10) and [(4-tBu-2,6-{P(O) (OiPr) ₂}₂C₆H₂SnCl)₃Pt(SnCl ₃)₂] (11). The compounds were characterised by elemental analyses, ¹H, ¹³C, ³¹P, ¹¹⁹Sn and ¹⁹⁵Pt NMR spectroscopy, single-crystal X-ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1, 3 and 4, also by Moessbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal-bipyramidal environment. The Moessbauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me₂NCH₂) ₂C₆H₃SnCl}₂PdCl₂]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands. Copyright

Full text of DOI:10.1002/chem.201203511

FULL PAPER
DOI: 10.1002/chem.201203511
Insights into the Intramolecular Donor Stabilisation of Organostannylene
Palladium and Platinum Complexes: Syntheses, Structures and
DFT ACTHNUGRTENUNGCalculations**
Michael Wagner,[a] Vajk Deꢀky,[a] Christina Dietz,[a] Jana Martincovꢀ,[b]
Bernard Mahieu,[d] Roman Jambor,*[b] Sonja Herres-Pawlis,*[a, c] and Klaus Jurkschat*[a]
Dedicated to Professor Dainis Dakternieks on the occasion of his 65th birthday
Abstract: The syntheses of the transi-
tion metal complexes cis-[(4-tBu-2,6-
{P(O)ACHTUNGTRENNUNG(OiPr)2}2C6H2SnCl)2MX2] (1, M=
Pd, X=Cl; 2, M=Pd, X=Br; 3, M=
Pd, X=I; 4, M=Pt, X=Cl), cis-[{2,6-
(Me2NCH2)2C6H3SnCl}2MX2] (5, M=
Pd, X=I; 6, M=Pt, X=Cl), trans-
The compounds were characterised by
elemental analyses, 1H, 13C, 31P, 119Sn
and 195Pt NMR spectroscopy, single-
crystal X-ray diffraction analysis, UV/
Vis spectroscopy and, in the cases of
compounds 1, 3 and 4, also by Mçss-
AHCTUNGTRENNbGUN auer spectroscopy. All the compounds
show the tin atoms in a distorted trigo-
nal-bipyramidal environment. The
MçssACTHNGUETRNNUbG auer spectra suggest the tin
atoms to be present in the oxidation
state III. The kinetic lability of the
complexes was studied by redistribu-
tion reactions between compounds 1
and 3 as well as between 1 and cis-
[{2,6-(Me2NCH2)2C6H3SnCl}2PdCl2].
DFT calculations provided insights into
both the bonding situation of the com-
pounds and the energy difference be-
tween the cis and trans isomers. The
latter is influenced by the donor
strength of the pincer-type ligands.
[{2,6-(Me2NCH2)2C6H3SnI}2PtI2]
(7)
(OiPr)2}2
C6H2ACHTUNGTRENNUNGSnCl)PdI2]2 (8) are reported. Also
and
trans-[(4-tBu-2,6-{P(O)ACHTNUGTRENNNUG
reported is the serendipitous formation
of the unprecedented complexes trans-
Keywords: density functional calcu-
lations · palladium · platinum ·
structure elucidation · tin · transi-
tion metals
[(4-tBu-2,6-{P(O)
Pt(SnCl3)2] (10) and [(4-tBu-2,6-{P(O)
(OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] (11).
ACHTUNGTRENNUNG(OiPr)2}2AHCTNURTGEGCNNUN 6H2ACTHNUGTRENSNUGN nCl)2
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
[a] M. Wagner,+ V. Deꢀky,+ C. Dietz, S. Herres-Pawlis, K. Jurkschat
Lehrstuhl fꢁr Anorganische Chemie II
Introduction
Technische Universitꢂt Dortmund, 44221 Dortmund (Germany)
Fax: (+49)231-755-5048
E-mail: klaus.jurkschat@tu-dortmund.de
One important characteristic of tin(II) compounds is their
lone electron pair,[1] which makes both inorganic as well as
organically substituted tin compounds interesting ligands for
Lewis acids such as transition metals.[2] The topic of transi-
tion metal complexes bearing SnII-based ligands has become
an active area of research and a vast number of transition
metal complexes containing stannylenes have been report-
ed.[3–24] In the last few decades, complexes with palladium or
platinum have gained considerable interest,[25–38] probably
due to the fact that tin(II) chloride, as the simplest example
of SnII-based ligands, is an important co-catalyst in various
group-10 metal-catalysed reactions such as hydroformyla-
tion,[39] hydrogenation,[40] isomerisation[41] or hydrogen-medi-
ated reductive coupling reactions.[42]
[b] J. Martincovꢀ, R. Jambor
Department of General and Inorganic Chemistry
University of Pardubice, Studentska 95
532 10, Pardubice (Czech Republic)
Fax: (+420)466037068
E-mail: roman.jambor@upce.cz
[c] S. Herres-Pawlis
Department Chemie, Ludwig-Maximilians-Universitꢂt Mꢁnchen
Butenandtstrasse 5–13, 81377 Mꢁnchen (Germany)
E-mail: sonja.herres-pawlis@cup.uni-muenchen.de
[d] B. Mahieu
Laboratoire de Chimie Physique Molꢃculaire et
de Cristallographie (CPMC)
1348 Louvain-la-Neuve (Belgium)
[+] M.W. and V.D. contributed equally to this work.
[**] Parts of this work were first presented at 13 Vortragstagung der
Wçhler-Vereinigung fꢁr Anorganische Chemie der GDCh, September
18–19, 2006, Aachen (Germany), Book of Abstracts P078, and the
13th International Symposium on Inorganic Ring Systems (IRIS),
July 29 to August 2, 2012, Victoria, Canada, Book of Abstracts O53.
The synthesis of palladium or platinum complexes is usu-
ally accompanied by the insertion of stannylenes SnR2 into
metal chloride bonds providing complexes containing
weakly coordinated [SnR2Cl]ꢀ anions with a trans labilising
effect although the importance and exact role of SnR2 as a
co-catalyst is still unclear.[43] Besides these, there are a few
examples in which the stannylenes behave as a s donor, as
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201203511. ORTEP drawings of
2 and 3, 31P and 119Sn NMR spectra of the redistribution reactions,
MO diagram of 4, bond critical points for [PtCl2ACTHNUTRGNENU(G SnClH)2], ball-and-
shown in A,[34,35] B,[28,29] C,[36]
D
[25] and E[44] (Scheme 1).
stick representation of the effect of the toluene solvate molecule on
the pincer-ligand backbone (aromatic ring) in 4·1.5C7H8 and coordi-
nates of calculated complexes.
Most of these complexes contain stannylene ligands bear-
ing bulky substituents, for example, (Me3Si)2N,[28,29]
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6695

tin(II) compounds and we were
interested in learning whether
heteroleptic organostannylenes,
like phosphane ligands, com-
plex palladium and platinum
halides as s donors without in-
ꢀ
serting into the M X bond.
Herein we present a number of
such complexes and investigate
their structures in solution and
in the solid state as well as their
reactivity. We complemented
the experimental work by per-
forming DFT calculations to
shed light on the chemical
bonding in these complexes. We
Scheme 1. Randomly selected examples of tin(II) complexes of palladium and platinum.
(Me3Si)2CH[33] and Me2Si
N
also report attempts to obtain complexes with higher nucle-
arity.
shown that anionic main-group element donors such as
(SnB11H11)ꢀ or [MeSi (aryl)}3Sn]ꢀ are also able to
ACTHNUTRGENNUG{SiMe2NACHTUNGTRENNUGN
bind various transition metals.[8,45]
A search of the Cambridge Crystallographic Data Base
and the literature for tin-containing platinum complexes re-
vealed that the majority of structures contain Sn/Pt ratios of
1:1[44d] and 2:1. There are only six compounds with a Sn/Pt
ratio of 3:1,[25,30,46] seven compounds with a Sn/Pt ratio of
4:1[26,45a,b,l,47] and three compounds with a Sn/Pt ratio of
5:1.[44] Notably, with the exceptions of compound F[26]
Results and Discussion
The reaction of the heteroleptic organostannylenes RSnCl
(R=4-tBu-2,6-[P(O)
G
2,6-(Me2NCH2)2C6H3)
with palladium and platinum dihalides MX2 (M=Pd, Pt;
X=Cl, Br, I) provided the corresponding cis transition
metal complexes 1–6 (Scheme 3) in good yields whereas,
under the same conditions, no reaction was observed with
nickel dihalides NiX2 (X=Cl, Br). The reaction in THF of
(SnCl2NAr)2SiMe2],[45l]
(Scheme 1) and [{Me2SiACHTNUGTRENNUG(ArN)2Sn}2PtACHTUNGTRENNUGN
each of the platinum complexes mentioned above contains
only one type of tin ligand.
4-tBu-2,6-[P(O)ACTHNUTRGENNUG(OiPr)2]2C6H2SnCl with [NiACHTUNGTREN(NNGU PPh3)2Cl2] in a
In addition to the examples given in Scheme 1, we have
shown that heteroleptic organostannylenes containing
Y,C,Y-coordinating pincer-type ligands R1 (Y=N) or R2
(Y=O) are able to complex a variety transition metals
(Scheme 2).[48]
molar ratio of 2:1 gave, after heating the reaction mixture at
reflux, metallic nickel and the organotin trichloride 4-tBu-
2,6-[P(O)ACHTUNRGTENUNG(OiPr)2]2C6H2SnCl3.
The reaction of the platinum dichloride complex 6 with
sodium iodide provided the complex trans-[{2,6-
The presence of N!Sn and O!Sn intramolecular coordi-
(Me2NCH2)2C6H3SnI}2PtI2] (7) as a crystalline material
(Scheme 3).
nation in the organochloridostannylenes 2,6-(Me2NCH2)2-
A
E
E
Notably, the reaction that gave compound 3 also provided
the 1:1 complex trans-[(4-tBu-2,6-{P(O)(OiPr)2}2AC6H2ASnCl)-
PdI2]2 (8) as by–product
tively, should increase the Lewis base capacity of these
G
E
CHTUNGTRENNUNG
N
a
(Scheme 4). Changing the stoi-
chiometry of the reaction to
1:1, however, did not increase
the yield of complex 8.
Moreover, compounds 2 and
3 were also obtained by the re-
action of 2 molequiv of 4-tBu-
2,6-[P(O)ACHTUNGTREN(UNG OiPr)2]2C6H2SnX
(X=Br, I) with PdCl2, which
indicates halogen exchange be-
tween the tin and palladium
atoms (Scheme 5) with the
latter preferring the softer
halide anions bromide and
iodide.
The complexes are yellow (1,
4, 6) or red (2, 3, 5, 7) crystal-
Scheme 2. Examples of transition-metal complexes with intramolecularly coordinated tin(II) compounds.
6696
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708

Organostannylene Palladium and Platinum Complexes
FULL PAPER
solvates, 1·C6H6, 2·C7H8, 3·C7H8, 4·1.5C7H8 and 7·2CHCl3,
were obtained from solutions of the corresponding solvents.
The molecular structures of complexes 1·C6H6, 4·1.5C7H8,
5, 6, 7·2CHCl3 and 8 are shown in Figures 1–6 and those of
complexes 2·C7H8 and 3·C7H8 are given in the Supporting
Information (see Figures S1 and S2). Selected interatomic
distances and angles for complexes 1–7 are collected in
Table 1 and Table 2, those of 8 are given in the caption to
Figure 6.
Scheme 3. Synthesis of the cis-configured complexes 1, 2 and 4–6 and the
trans-configured complex 7.
Figure 1. Molecular structure of 1·C6H6. Displacement ellipsoids are
drawn at the 30% probability level. The benzene solvate molecule and
all methyl groups have been omitted for clarity.
Scheme 4. Synthesis of the cis-configured complex 3 and the formation of
Figure 2. Standard ball-and-stick model of 4·1.5C7H8. The toluene solvate
the 1:1-complex trans-[(4-tBu-2,6-{P(O)ACTHNUGTRNEUNG(OiPr)2}2C6H2SnCl)PdI2]2 (8) as a
molecules and all methyl groups have been omitted for clarity.
byproduct.
Scheme 5. Alternative synthesis of complexes 2 and 3.
line solids and are readily soluble in common organic sol-
vents such as toluene, dichloromethane and THF, but poorly
soluble in n-hexane. Complex 8 is a deep-red crystalline
solid that is only poorly soluble in toluene but readily solu-
ble in dichloromethane.
Figure 3. Molecular structure of 5. Displacement ellipsoids are drawn at
the 30% probability level. Symmetry code: (a) x, y, ꢀz.
Single crystals of complexes 1–8 suitable for X-ray diffrac-
tion analysis, some as their benzene, toluene or chloroform
Notably, the palladium and platinum atoms in compounds
1–6 adopt cis square-planar environments in which the orga-
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6697

R. Jambor, S. Herres-Pawlis, K. Jurkschat et al.
The Sn(1) and Sn(2) atoms are pentacoordinated and
each show a strongly distorted trigonal-bipyramidal environ-
ment with C(1)/C(11), X(1)/X(2) and M(1) (1, X=Cl, M=
Pd; 2, X=Br, M=Pd; 3, X=I, M=Pd; 4, X=Cl, M=Pt; 5,
X=I, M=Pd; 6, X=Cl, M=Pt) occupying the equatorial
positions and the oxygen and nitrogen atoms O(1) and O(2)
(1–4), O(3) and O(4) (1, 2, 4), and N(1) and N(2) (5, 6) oc-
cupying the axial positions. The distortion from the ideal ge-
ometry is especially manifested by the equatorial angles,
which vary between 94.75(8) (C(1)-Sn(1)-Cl(1), 3) and
138.6(1)8 (C(1)-Sn(1)-Pt(1), 6), and the axial angles, which
vary between 147.8(2) (N(1)-Sn(1)-N(2), 5) and 157.1(2)8
(O(3)-Sn(2)-O(4), 2). These two latter angles clearly result
from ligand constraint, which appears to be more pro-
nounced for the dimethylaminomethyl-substituted pincer-
type ligand. The deviation of the equatorial angles from
1208 is a result of the differences in the steric bulk of the
halogen atoms, the metal atoms and the organic substituents.
The platinum complex 4 shows the smallest C(1)-Sn(1)-
M(1) angle of 126.9(3)8.
Figure 4. Molecular structure of 6. Displacement ellipsoids are drawn at
the 30% probability level. Symmetry code: (a) x, y, ꢀz.
ꢀ
ꢀ
The Sn O distances vary between 2.272(9) (Sn(1) O(1),
ꢀ
ꢀ
4) and 2.339(3) ꢅ (Sn(2) O(3), 1), and the Sn N distances
ꢀ
ꢀ
between 2.437(7) (Sn(1) N(1), 5) and 2.534(7) ꢅ (Sn(1)
N(2), 5). The Sn Cl distances vary between 2.380(1)
(Sn(1) Cl(1), 4) and 2.493(3) ꢅ (Sn(1) Cl(1), 2). The latter
distance and that of 2.470(2) ꢅ (5) are close to those of the
ꢀ
Figure 5. Molecular structure of 7·2CHCl3. Displacement ellipsoids are
drawn at the 30% probability level. The chloroform solvate molecules
have been omitted for clarity. Symmetry code: (a) ꢀx, ꢀy, ꢀz.
ꢀ
ꢀ
parent organochloridostannylenes 4-tBu-2,6-[P(O)ACHTUNGTRENNUNG(OiPr)2]2
C6H2SnCl (2.4708(8) ꢅ)[51,52] and 2,6-(Me2NCH2)2C6H3SnCl
(2.488(3) ꢅ).[53]
nostannylene ligands coordinate the transition metal atoms
ꢀ
through their lone electron pair. The Pd Sn distances vary
In complexes 1–6, the organostannylenes RSnCl (R=4-
tBu-2,6-[P(O)ACHTNGUTERNU(NG OiPr)2]2C6H2, 2,6-(Me2NCH2)2C6H3) are mu-
ꢀ
ꢀ
between 2.464(1) (Pd1 Sn2, 2·C7H8) and 2.5138(9) ꢅ (Pd1
ꢀ
ꢀ
Sn1, 5) and the Pt Sn distances vary between 2.469(1) (Pt1
Sn1, 4·C7H8) and 2.4865(4) ꢅ (6). These values are close to
tually cis coordinated with the Sn-M-Sn angles ranging be-
tween 96.37(2) (1) and 100.33(2)8 (6). A rather interesting
feature in the structures of complexes 1–6 is the intramolec-
ular Sn···Sn distance, which ranges between 3.682(1) (1) and
3.837(1) ꢅ (5) and which is shorter than twice the van der
those reported for other tin-containing platinum and palladi-
um complexes.[25,26,44,45l,46,47,49] Interestingly, the Pd Sn dis-
ꢀ
tances are somewhat shorter than the distances given by
Pyykkç and Atsumi for single Pd Sn bonds (2.6 ꢅ).
[50]
ꢀ
Table 1. Selected bond lengths [ꢅ] for compounds 1–7.
1·C6H6
2·C7H8
3·C7H8
4·1.5C7H8
5
6
7·2CHCl3
M=Pd, X=Cl
M=Pd, X=Br
M=Pd, X=I
M=Pt, X=Cl
M=Pd, X=I
M=Pt, X=Cl
M=Pt, X=I
ꢀ
Sn(1) C(1)
2.171(4)
2.304(3)
2.302(3)
2.145(10)
2.325(6)
2.302(6)
2.159(3)
2.326(2)
2.335(2)
2.172(13)
2.272(9)
2.295(8)
2.128(8)
2.115(5)
2.112(6)
ꢀ
Sn(1) O(1)
ꢀ
Sn(1) O(2)
ꢀ
Sn(1) N(1)
2.437(7)
2.534(7)
2.470(2)
2.487(4)
2.439(4)
2.3828(15)
2.467(5)
2.526(5)
ꢀ
Sn(1) N(2)
ꢀ
Sn(1) Cl(1)
2.390(1)
2.493(3)
2.398(1)
2.380(1)
ꢀ
Sn(1) I(1)
2.7672(6)
2.5532(5)
ꢀ
Sn(1) M(1)
2.4742(5)
2.175(4)
2.339(3)
2.314(3)
2.391(1)
2.4659(5)
2.474(1)
2.146(9)
2.361(6)
2.291(6)
2.464(3)
2.464(1)
2.4945(3)
2.469(1)
2.186(14)
2.318(9)
2.316(8)
2.388(4)
2.476(1)
2.5138(9)
2.4865(4)
ꢀ
Sn(2) C(11)
ꢀ
Sn(2) O(3)
ꢀ
Sn(2) O(4)
ꢀ
Sn(2) Cl(2)
ꢀ
Sn(2) M(1)
ꢀ
M(1) X(1)
2.6581(9)
ꢀ
M(1) X(2)
2.391(1)
2.5837(4)
ꢀ
M(1) X(3)
2.363(1)
2.376(1)
2.474(2)
2.481(2)
2.6545(3)
2.363(3)
2.355(3)
ꢀ
M(1) X(4)
6698
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708

Organostannylene Palladium and Platinum Complexes
FULL PAPER
Table 2. Selected bond angles [8] for compounds 1–7.
1·C6H6
M=Pd
X=Cl
Y=Cl
2·C7H8
M=Pd
X=Br
Y=Cl
3·C7H8
M=Pd
X=I
4·1.5C7H8
M=Pt
X=Cl
5
6
7·2CHCl3
M=Pt
X=I
M=Pd
X=I
Y=Cl
M=Pt
X=Cl
Y=Cl
Y=Cl
Y=Cl
Y=I
C(1)-Sn(1)-M(1)
C(1)-Sn(1)-Y(1)
M(1)-Sn(1)-Y(1)
O(1)-Sn(1)-O(2)
C(11)-Sn(2)-M(1)
C(11)-Sn(2)-Y(2)
M(1)-Sn(2)-Y(2)
O(3)-Sn(2)-O(4)
Sn(1)-M(1)-Sn(2)
Sn(1)-M(1)-X(3)
Sn(2)-M(1)-X(4)
X(3)-M(1)-X(4)
N(1)-Sn(1)-N(2)
Sn(1)-M(1)-Y(1)
Y(1)-M(1)-Y(1a)
134.67(9)
95.88(9)
129.14(3)
156.65(9)
137.76(9)
94.7(1)
127.43(3)
156.72(8)
96.37(2)
83.93(3)
79.80(3)
99.64(4)
136.9(2)
95.6(2)
127.11(7)
156.6(2)
137.1(2)
94.0(2)
128.86(7)
157.1(2)
97.23(4)
84.36(5)
79.33(4)
98.85(5)
135.95(8)
94.75(8)
129.30(2)
156.89(7)
126.9(3)
101.1(3)
132.0(1)
156.7(3)
128.5(3)
102.7(3)
128.8(1)
156.3(3)
99.88(4)
83.13(9)
83.65(8)
93.4(1)
137.5(2)
98.6(2)
123.90(5)
138.6(1)
98.74(14)
122.63(4)
138.2(2)
101.8(2)
119.72(2)
98.55(2)
81.228(9)
99.49(4)
100.33(2)
180.0
98.99(2)
147.8(2)
82.40(2)
96.02(4)
148.7(1)
82.53(3)
94.62(7)
148.2(2)
86.57(2)
180.0
atoms being trans to each other.
The I(1) and I(1a) atoms are
also in a trans disposition. The
ꢀ
Pt(1) Sn(1)
distance
of
2.5532(5) ꢅ is longer than the
corresponding distances in the
cis-configured complexes
(2.469(1) ꢅ) and
4
6
(2.4865(4) ꢅ). The same holds
ꢀ
ꢀ
for the Sn(1) N(1) and Sn(2)
N(2) distances of 2.467(5) and
2.526(5) ꢅ, respectively, which
are longer than the correspond-
ing distances in 6. From the
data at hand, however, it is not
evident whether these effects
are exclusively the result of the
trans configuration in complex
7·2CHCl3 as the cis-configured
Figure 6. Standard ball-and-stick model of the molecular structure of 8. All methyl groups have been omitted
ꢀ
for clarity. Symmetry code: (a) ꢀx+1, ꢀy, ꢀz+2. Selected interatomic distances [ꢅ]: Sn(1) Pd(1) 2.4804(15),
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Pd(1) I(1) 2.5866(16), Pd(1) I(2) 2.5829(16), Pd(1) I(1a) 2.6867(15), Sn(1) O(1) 2.312(9), Sn(1) O(2)
ꢀ
ꢀ
2.272(8), Sn(1) Cl(1) 2.419(4), Sn(1) C(1) 2.147(15). Selected interatomic angles [8]: I(1)-Pd(1)-I(2) 175.41(6),
Sn(1)-Pd(1)-I(1a) 175.82(7), I(1)-Pd(1)-I(1a) 88.99(5), Pd(1)-I(1)-Pd(1a) 91.01(5), O(1)-Sn(1)-O(2) 156.6(3),
C(1)-Sn(1)-Cl(1) 102.3(4), C(1)-Sn(1)-Pd(1) 135.5(4), Cl(1)-Sn(1)-Pd(1) 121.62(10).
complexes
4 and 6 contain
chlorido instead of iodido sub-
stituents.
Complex 8 is a centrosymmetric trans-configured dimer
Waals radius of tin (2.20 ꢅ).[54] DFT calculations (see
below) suggest that these are bonding interactions.
The Mçssbauer spectra of compounds 3 and 4 show
isomer shifts (ISs) of 1.81 (quadrupole splitting, QS=
3.51 mmsꢀ1) and 1.70 mmsꢀ1 (QS=3.48 mmsꢀ1), respective-
ly. These IS values are very unusual and lie out of the range
ꢀ
containing non-symmetric m-iodido bridges at Pd(1) I(1)
ꢀ
and Pd(1) I(1a) distances of 2.587(2) and 2.687(2) ꢅ, re-
ꢀ
spectively. Notably, the Pd(1) I(2) distance (2.583(2) ꢅ) in-
volving a non-bridging iodine atom is almost identical to the
ꢀ
corresponding distance Pd(1) I(1) involving
a bridging
generally observed for organo
N
iodine atom. The Sn(1) atom, as in compounds 1–4, shows a
distorted trigonal-bipyramidal environment with the intera-
tomic distances and angles being close to those of 1–4. In
contrast to compounds 1–6, but similarly to the iodido sub-
stituents at the tin atoms in 7·2CHCl3, the chlorido substitu-
ents in 8 are mutually trans to each other.
and organotin(IV) compounds (1.1–1.6 mmsꢀ1),[56] which
suggests that the tin atoms in 3 and 4 have an oxidation
state of III. This view is correct when considering mainly co-
valent bonds to the three more electronegative carbon,
chlorine or iodine, and palladium atoms. It is also supported
by the natural bond order (NBO) calculations (see below).
The Pt(1) atom in 7·2CHCl3 exhibits a perfect square-
planar environment with the Sn(1)/Sn(1a) and I(2)/I(2a)
The structures of complexes 1–6 are retained in solution.
Thus, the 31P NMR spectra of compounds 1–4 recorded in
[57]
CD2Cl2 show, with respect to the parent organochlorido
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6699

R. Jambor, S. Herres-Pawlis, K. Jurkschat et al.
1
stannylene 4-tBu-2,6-[P(O)
N
Thus, the H NMR spectrum of 7 in CDCl3 at room temper-
ature shows single resonances for the NCH2 (d=4.13 ppm)
and NCH3 (d=2.88 ppm) protons. No decoalescence phe-
nomena were observed at 270 K. Measurements at lower
temperature failed as a result of the rather poor solubility of
compound 7. The 119Sn NMR spectrum of compound 7
shows a single resonance at d=ꢀ80 ppm, which is consider-
ably high-frequency shifted compared with the cis-config-
ured complex 6 (d=ꢀ254 ppm) it was synthesised from. The
31P NMR spectrum of 8 recorded in CD2Cl2 shows two reso-
nances at d=26.2 (J(31P, 117/119Sn)=186 Hz, integral 2) and
26.3 ppm (J(31P, 117/119Sn)=172 Hz integral 1), which indicates
that compound 8 disintegrates. This was not investigated fur-
ther.
J(31P, 117/119Sn)=120 Hz), low-frequency shifted singlet reso-
nances falling in the narrow range of d=27.5 (1, 4) and
28.0 ppm (3). They are flanked by 117/119Sn satellites ranging
between 126 Hz (unresolved) for the platinum dichlorido
complex 4 and 184/192 Hz for the palladium diiodido com-
plex 3. Notably, there are also unresolved 4J(31P, 117/119Sn)
couplings of 24 (1) and 27 Hz (2, 3). Moreover, the spectrum
of complex 4 also shows J(31P, 195Pt) satellites of 126 Hz that
are superimposed on the 117/119Sn satellites giving rise to a
total satellite-to-signal-to-satellite integral ratio of 24:52:24,
which is close to the calculated ratio. The 119Sn NMR spectra
recorded in CD2Cl2 show triplet-of-triplet resonances at d=
ꢀ363 (J(119Sn,31P)=186, 24 Hz, J(119Sn,117Sn)=4490 Hz, 1),
ꢀ321 (J(119Sn,31P)=178, 27 Hz, J(119Sn,117Sn)=5640 Hz, 2)
and ꢀ257 ppm (J(119Sn,31P)=192, 27 Hz, J(119Sn,117Sn)=
Redistribution reactions: The 31P NMR spectrum (see Fig-
ure S3 in the Supporting Information) of a solution contain-
ing equimolar quantities of the palladium dichloride com-
plex 1 and the palladium diiodide complex 3 in C6D6 shows
four almost equally intense resonances at d=29.2 (integral
29%, J(31P, 117/119Sn)=195 Hz, 3), 29.1 (integral 26%, J(31P, 119/
117Sn)=204 Hz, signal a), 29.0 (integral 24%, J(31P, 117/
119Sn)=178 Hz, signal b) and 28.8 ppm (integral 21%,
J(31P, 117/119Sn)=182 Hz, 1). The 119Sn NMR spectrum (see
Figure S4 in the Supporting Information) of the same solu-
tion displays four triplet resonances at d=ꢀ257 (integral
33%, J(119/117Sn,31P)=195 Hz, 3), ꢀ301 (integral 26%, J(119/
117Sn,31P)=205 Hz, signal c), ꢀ327 (integral 22%, J(119/
117Sn,31P)=178 Hz, signal d) and ꢀ365 ppm (integral 20%,
J(119/117Sn,31P)=205 Hz, 1). These spectra indicate halogen
exchange between the palladium atoms and the in situ for-
6480 Hz, 3) and
a
triplet resonance at d=ꢀ483 ppm
1
(J(119Sn,31P)=130 Hz, J(119Sn,195Pt)=28470 Hz, J(119Sn,117Sn)
=1500 Hz, 4), respectively, which is low-frequency shifted
with respect to 4-tBu-2,6-[P(O)ACHTUNRGTNE(UNG OiPr)2]2C6H2SnCl (d=
ꢀ99 ppm (J(119Sn,31P)=121 Hz),[51] as well as singlet reso-
nances at d=ꢀ20 (J(119Sn,117Sn)=3885 Hz, 5) and
ꢀ254 ppm (1J(119Sn,195Pt)=12640 Hz, 6), with the latter also
being low-frequency shifted with respect to the parent orga-
nostannylene 2,6-(Me2NCH2)2C6H3SnCl (d=156 ppm).[53]
Notably, the resonances for the complexes 1–4 are more
low-frequency shifted than those for complexes 5, 6 and cis-
[{2,6-(Me2NCH2)2C6H3SnCl}2PdCl2] (d=ꢀ122 ppm).[48g] This
hints at a stronger intramolecular P=O!Sn coordination in
1–4 compared with the N!Sn interaction in 5 and 6. A
striking feature of the 119Sn NMR spectra of complexes 1–3
and 5 is the observation of large J(119Sn,117Sn) couplings in
the range 3885 (5) and 6480 Hz (3). The magnitude of the
coupling depends on both the nature of the intramolecularly
coordinating donor atom (P=O!Sn in 1 versus N!Sn in 5)
and the halogen substituents at the palladium atom with the
largest coupling observed for the palladium diiodide com-
plex 3. With caution we interpret these couplings as being
mation of the complex cis-[(4-tBu-2,6-{P(O)
ACHTUNGRTEN(NUNG OiPr)2}2-
AHCTUNGTRENNUNG
complex.
The 31P NMR spectrum of a solution of complex 1 in
C6D6 to which had been added 2 molequiv of triphenylphos-
1
phane shows broad resonances at d=37.8 (n = =143 Hz, 4-
2
1
tBu-2,6-[P(O)ACHTUNGTRNENG(U O-iPr)2]2C6H2SnCl), 28.8 (n = =220 Hz, 1) and
2
1
2
1
composed of J and J with both showing the same sign.
The 195Pt NMR spectrum of complex 4 shows a quintet
resonance at d=ꢀ4482 ppm (J(195Pt,31P)=122 Hz, J(195Pt,117/
119Sn)=27190/28480 Hz).
ꢀ3.8 ppm (n = =107 Hz, Ph3P).
2
The 31P NMR spectrum of a solution of complex 1 in
C6D6 to which had been added 2 molequiv of 4-tBu-2,6-
[P(O)ACTHNUGRTNEUNG(OiPr)2]2C6H2SnCl shows rather broad resonances
1
As in the chromium–pentacarbonyl complex [4-tBu-2,6-
with equal integrals at d=37.4 (n = =270 Hz, 4-tBu-2,6-
2
1
{P(O)
(OiPr)2}2C6H2(Cl)SnCr(CO)5],[51,58] the H NMR spec-
[P(O)
(OiPr)2]2C6H2SnCl) and d=28.8 ppm (n = =216 Hz, 1).
1
2
tra of complexes 1–4 each show four doublet resonances for
the isopropyloxy methyl protons. Exemplarily, the spectrum
of a solution of complex 4 in [D8]toluene was recorded at
808C. No coalescence phenomena were observed, which in-
dicates high configurational stability of the tin atoms. As in
the related complex [2,6-(Me2NCH2)2C6H3(H)SnW(CO)5],[59]
The 119Sn NMR spectrum of the same solution displays only
1
one broad resonance at d=ꢀ366 ppm (n = =520 Hz). The
2
ꢀ
spectra indicate kinetic lability of the Pd Sn bond in com-
plex 1 and suggest the possibility of replacing one organo-
stannylene moiety by another one or by other ligands.
This idea was confirmed by recording time-dependent
31P NMR spectra of a solution of equimolar amounts of
complex 1 and cis-[{2,6-(Me2NCH2)2C6H3SnCl}2PdCl2] in
CDCl3. The spectrum recorded 1 h after the solution had
been prepared displays a major sharp resonance at d=
28.3 ppm (J(31P, 117/119Sn)=176, 21 Hz, signal e). In addition,
there is a minor intense signal (approx. 5%) at d=27.8 ppm
belonging to residual amounts of complex 1. The 119Sn NMR
1
the H NMR spectra of complexes 5 and 6 each exhibit two
equally intense singlet resonances for the N-methyl protons
and AB-type resonances for the methylene protons. These
observations indicate the tin atoms in these compounds to
be configurationally stable as well.
In solution, the intramolecular N!Sn coordination in
1
compound 7 is kinetically labile on the H NMR timescale.
6700
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708

Organostannylene Palladium and Platinum Complexes
FULL PAPER
spectrum of the same solution shows a singlet resonance f at
d=ꢀ125 ppm (J(119Sn,117/119Sn)=3942 Hz) and a triplet reso-
nance g at d=ꢀ335 ppm (J(119Sn,31P)=174 Hz, J(119Sn,117/
119Sn)=3921 Hz) with an integral ratio of 1:1. The signals
The molecular structure of complex 10·2C7H8 is shown in
Figure 7 and selected interatomic distances and angles are
given in the caption. The Pt(1) atom in 10·2C7H8 is four-co-
e–g were assigned to the complex [{2,6-(Me2NCH2)
2ACHTUGNRTENCNUNG 6H3-
A
ACHTUNGTRENNUNG
ing two different organostannylene ligands. From the data at
hand, however, it is not clear whether complex 9 has a cis or
trans configuration. The 119Sn NMR spectrum of this solu-
tion to which
a
further amount of cis-[{2,6-
(Me2NCH2)2C6H3SnCl}2PdCl2] had been added shows, in ad-
dition to the resonances for 9, a resonance at d=ꢀ122 ppm
belonging to the former complex. Apparently the non-sym-
metrically substituted complex 9 is thermodynamically fav-
oured over the symmetrically substituted complexes. How-
ever, so far, attempts to isolate complex 9 as an analytically
pure material have failed.
Serendipitous formation of the penta- and hexanuclear com-
plexes 10 and 11: In the complexes 1–8 discussed above, the
heteroleptic organostannylene ligands act as s donors to-
wards the platinum atom. On the other hand, there are nu-
merous platinum complexes that contain the [SnCl3]ꢀ ligand
Figure 7. Standard ball-and-stick model of 10·2C7H8. The toluene solvate
molecules and all methyl groups have been omitted for clarity. Symmetry
ꢀ
code: (a) ꢀx, ꢀy, z. Selected interatomic distances [ꢅ]: Pt(1) Sn(1)
ꢀ
ꢀ
ꢀ
2.5460(6), Pt(1) Sn(2) 2.5352(6), Sn(1) O(1) 2.303(7), Sn(1) O(2)
ꢀ
ꢀ
ꢀ
2.278(7), Sn(1) Cl(1) 2.392(3), Sn(1) C(1) 2.171(7), Sn(2) Cl(2)
ꢀ
ꢀ
2.378(3), Sn(2) Cl(3) 2.340(4), Sn(2) Cl(4) 2.338(4). Selected interatom-
ic angles [8]: Sn(1)-Pt(1)-Sn(1a) 172.84(8), Sn(2)-Pt(1)-Sn(2a) 173.95(9),
O(1)-Sn(1)-O(2) 155.5(2), C(1)-Sn(1)-Cl(1) 91.7(3), C(1)-Sn(1)-Pt(1)
157.4(2), Cl(1)-Sn(1)-Pt(1) 110.59(7).
as
a result of the insertion of tin(II) chloride into
[44]
ꢀ
Pt Cl bonds. These observations suggest that it should be
possible to obtain platinum complexes containing both types
of ligands at the same time.
The 31P NMR spectrum of a solution (A) of compound 4
and tin(II) chloride (molar ratio of 1:2) in CD2Cl2 shows a
major resonance at d=29.85 ppm (integral approx. 58%)
that is flanked by satellites of 87 Hz. The satellite-to-signal-
to-satellite ratio of 14:30:14 indicates these satellites to be
the superposition of J(31P, 117/119Sn) and J(31P, 195Pt) (calculated
ratio: 25:50:25). In addition, there are six minor intense res-
onances at d=29.0, 28.8, 28.4, 28.3, 27.6 and 27.0 ppm (total
integral approx. 36%). The 119Sn NMR spectrum of the
same solution shows, even after extensive data acquisition
(10240 scans), a rather noisy spectrum in which at least 10
resonances at d=ꢀ48, ꢀ67, ꢀ122, ꢀ150, ꢀ234, ꢀ336, ꢀ396,
ꢀ484, ꢀ504 and ꢀ550 ppm were identified. The 31P NMR
spectrum of a clear deep-red solution (B) of compound 4
and SnCl2 (molar ratio of 1:3) in C6D6 shows a single reso-
nance at d=30.00 ppm flanked by satellites of 87 Hz with
the satellite-to-signal-to-satellite ratio as above. From this
solution no 119Sn NMR signals could be detected. So far, all
attempts to obtain a pure compound from this solution have
failed. However, from the many experiments with reaction
mixtures containing platinum dichloride, tin dichloride and
ordinate and exhibits a slightly distorted square-planar envi-
ronment with the Sn(1)/Sn(1a) and Sn(2)/Sn(2a) atoms mu-
tually trans to each other. The deviation of the Sn(1)-Pt(1)-
Sn(1a) and Sn(2)-Pt(1)-Sn(2a) angles from 1808 might be
the result of steric congestion and/or additional weak intra-
molecular Cl(2)···Sn(1) and Cl(1)···Sn(2) interactions at dis-
tances of 3.511(1) and 3.602(1) ꢅ, respectively, which are
shorter than the sum of the van der Waals radii[54] of tin
(2.20 ꢅ) and chlorine (1.70–1.90 ꢅ). Thus, the Sn(1) atom is
[5+1] coordinate and exhibits a distorted octahedral envi-
ronment with the O(1), O(2), C(1) and Pt(1) atoms occupy-
ing the equatorial positions and the Cl(1) and Cl(2) atoms
the axial positions, whereas the Sn(2) atom is [4+1] coordi-
nate and exhibits a distorted trigonal-bipyramidal environ-
ment. The Cl(1) atom approaches the Sn(2) atom at the tet-
rahedral face defined by Pt(1), Cl(3) and Cl(4). Both the
ꢀ
ꢀ
Pt(1) Sn(1) (2.5460(6) ꢅ) and Pt(1) Sn(2) (2.5352(6) ꢅ)
ꢀ
distances are slightly longer than the Pt(1) Sn(1) and
ꢀ
Pt(1) Sn(2) distances of 2.469(1) and 2.476(1) ꢅ, respective-
ly, in compound 4. The other distances and the bond angles
are rather similar to those in 4.
the organochloridostannylene 4-tBu-2,6-[P(O)
SnCl in a molar ratio of 1:2:2 or 1:3:2 we obtained, by crys-
tal picking, small quantities of the novel complexes [(4-tBu-
2,6-{P(O)(OiPr)2}2C6H2SnCl)nPt(SnCl3)2] (10·2C7H8, n=2;
ACHTUTNGRENG(NU OiPr)2]2ACHUTGNTRENCNUNG 6H2-
G
The molecular structure of 11·C7H8·0.5C6H14 is shown in
Figure 8 and selected interatomic distances and angles are
given in Tables 3 and 4. The Pt(1) atom is pentacoordinated
and exhibits a distorted trigonal-bipyramidal environment
with the aryl-bound Sn(2) and Sn(3) atoms occupying the
axial positions and the aryl-bound Sn(1) and the trichlorido-
substituted Sn(4) and Sn(5) atoms occupying the equatorial
positions. The distortion from ideal geometry is manifested
A
ACHTUNGTRENNUNG
11·C7H8·0.5C6H14, n=3) as red single crystals suitable for X-
ray diffraction analysis. So far, attempts at obtaining these
compounds by rational syntheses in bigger quantities have
failed.
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6701

R. Jambor, S. Herres-Pawlis, K. Jurkschat et al.
by the equatorial Sn(1)-Pt(1)-Sn(5) (115.84(2)8), Sn(1)-
Pt(1)-Sn(4) (127.95(2)8) and Sn(4)-Pt(1)-Sn(5) (116.19(2)8)
angles, which deviate from 1208. The axial Sn(2)-Pt(1)-Sn(3)
ꢀ
angle (178.06(2)8), however, is close to 1808. The Pt Sn dis-
ꢀ
tances fall in the narrow range between 2.5597(5) (Pt(1)
ꢀ
Sn(2)) and 2.5801(5) ꢅ (Pt(1) Sn(5)). Interestingly, the lon-
gest distance is observed for an equatorially and not an ax-
ially located tin atom. This observation is in line with find-
ings reported for [NHEt3]3[Pt
(SnCl3)5][44c] and [PtCl
ACHTUNGTRENNUNG
(SMe2)3]3[Pt
AHCTUNGTRENNUNG
trigonal-bipyramidal d8-configured transition metals accord-
ing to which axial bonds should be shorter than equatorial
ones.[60] The geometries around the tin atoms and the bond
lengths and angles within the organostannylene moieties re-
semble those discussed for compound 10·2C7H8. As for the
latter compound, the intramolecular Sn(2)···Cl(41) and
Sn(3)···Cl(52) distances of 3.634 (1) and 3.623(1) ꢅ, respec-
tively, are shorter than the sum of the van der Waals radii[54]
of tin and chlorine.
Figure 8. Molecular structure of 11·C7H8·0.5C6H14. Displacement ellip-
soids are drawn at the 30% probability level. The solvate molecules have
been removed by the Squeeze routine of the program Platon.[61] The
methyl groups have been omitted for clarity.
DFT calculations: To elucidate the bonding situa-
tion in complexes 1–7, DFT calculations were per-
formed. Turbomole[62] with the pure functional
BP86[63] and the def2-TZVP basis set[64] was used
for the geometry optimisation because this combi-
nation has already been employed for similar com-
pounds.[65] The calculated data for all seven com-
pounds are in good agreement with the experimen-
tal data (Tables 5 and 6). The energy differences be-
tween the cis and trans isomers have also been de-
termined (Table 7). In the case of the O,C,O-
coordinating pincer-type ligand-stabilised com-
Table 3. Selected bond lengths [ꢅ] for 11·C7H8·0.5C6H14.
ꢀ
Pt(1) Sn(1)
2.5613(5)
2.5597(5)
2.5635(5)
2.5806(5)
2.5801(5)
2.162(5)
2.318(4)
2.315(4)
2.441(4)
ꢀ
Pt(1) Sn(2)
ꢀ
Pt(1) Sn(3)
ꢀ
Pt(1) Sn(4)
ꢀ
Pt(1) Sn(5)
ꢀ
ꢀ
ꢀ
Sn(1) C(1)
Sn(2) C(11)
2.170(5)
2.277(3)
2.317(3)
Sn(3) C(21)
2.138(6)
2.342(4)
2.278(3)
2.406(7)
ꢀ
ꢀ
ꢀ
Sn(1) O(1)
Sn(2) O(11)
Sn(3) O(21)
ꢀ
ꢀ
ꢀ
Sn(1) O(2)
Sn(2) O(12)
Sn(3) O(22)
ꢀ
ꢀ
ꢀ
Sn(1) Cl(1)
Sn(2) Cl(2)
2.3787(17) Sn(3) Cl(3)
ꢀ
ꢀ
Sn(1) O
A
Sn(3) O
A
plexes 1–4, DFT predicts the cis isomers to be con-
siderably more stable than the trans-configured
complexes, whereas for complexes 5–7 containing
the N,C,N-coordinating pincer-type ligands, the
energy difference between the cis and trans isomers
is predicted to be rather small and at the limit of
significance of the calculations. From these calculations it
becomes understandable that, as shown in Scheme 2, trans-
[{2,6-(Me2NCH2)2C6H3SnI}2PtI2] (7) could be obtained from
the reaction of the platinum dichloride complex 6 with
sodium iodide.
ꢀ
ꢀ
Sn(4) Cl(41)
2.4129(16) Sn(5) Cl(51) 2.4068(16)
2.4082(16) Sn(5) Cl(52) 2.4307(16)
2.3737(18) Sn(5) Cl(53) 2.3903(17)
ꢀ
ꢀ
Sn(4) Cl(42)
ꢀ
ꢀ
Sn(4) Cl(43)
Table 4. Selected bond angles [8] for 11·C7H8·0.5C6H14.
Sn(1)-Pt(1)-Sn(2)
Sn(1)-Pt(1)-Sn(3)
Sn(1)-Pt(1)-Sn(4)
Sn(1)-Pt(1)-Sn(5)
Sn(2)-Pt(1)-Sn(3)
90.907(16)
89.947(16)
127.950(17)
115.841(17)
178.062(18)
97.3(6)
Sn(2)-Pt(1)-Sn(4)
Sn(2)-Pt(1)-Sn(5)
Sn(3)-Pt(1)-Sn(4)
Sn(3)-Pt(1)-Sn(5)
Sn(4)-Pt(1)-Sn(5)
90.325(16)
90.207(16)
87.778(16)
90.986(16)
116.186(17)
O
N
In further theoretical investigations, NBO calculations[66]
were performed with the BP86/def2-TZVP combination in
Gaussian 03[67] to gain an insight into the electronic struc-
O(2)-Sn(1)-O(1)
C(1)-Sn(1)-Cl(1)
C(1)-Sn(1)-Pt(1)
Cl(1)-Sn(1)-Pt(1)
O(11)-Sn(2)-O(12)
O(11)-Sn(2)-Cl(2)
C(11)-Sn(2)-Pt(1)
Cl(2)-Sn(2)-Pt(1)
155.43(13)
94.4(2)
139.64(15)
125.82(16)
156.56(12)
90.87(11)
143.67(15)
120.28(4)
ꢀ
tures of the complexes. The calculations reveal both the Sn
ꢀ
Pd and Sn Pt bonds to be highly covalent with an almost
O
N
97.8(7)
156.73(13)
92.8(3)
O(21)-Sn(3)-O(22)
C(21)-Sn(3)-Cl(3)
O
equal contribution from each bonding partner. The two de-
ꢀ
generate HOMO-90/91 MOs of the highly covalent Sn Pt
bonds in compound 4 are shown in Figure 9.
115.2(7)
146.04(15)
94.27(6)
95.45(6)
96.35(6)
127.30(4)
111.59(4)
124.39(4)
C(21)-Sn(3)-Pt(1)
Cl(51)-Sn(5)-Cl(52)
Cl(51)-Sn(5)-Cl(53)
Cl(52)-Sn(5)-Cl(53)
Cl(51)-Sn(5)-Pt(1)
Cl(52)-Sn(5)-Pt(1)
Cl(53)-Sn(5)-Pt(1)
ꢀ
The Wiberg bond index for the Sn M bond possesses
Cl(41)-Sn(4)-Cl(42)
Cl(41)-Sn(4)-Cl(43)
Cl(42)-Sn(4)-Cl(43)
Cl(41)-Sn(4)-Pt(1)
Cl(42)-Sn(4)-Pt(1)
Cl(43)-Sn(4)-Pt(1)
91.10(6)
94.10(6)
97.07(7)
113.75(4)
130.72(5)
121.10(5)
values between 0.62 (3) and 0.72 (4), whereas the donor sta-
bilisation of the pincer-type ligands is reflected by Wiberg
bond indices of 0.19 (1–3) to 0.23 (4) for P=O donors and
0.16 (5, 7) to 0.18 (6) for the nitrogen donors.
6702
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708

Organostannylene Palladium and Platinum Complexes
FULL PAPER
Table 5. Calculated bond lengths [ꢅ] for compounds 1–7 (BP86/def2-TZVP).
The molecular structures of
the square-planar complexes 1–
1
2
3
4
5
6
7
M=Pd
X=Cl
M=Pd
X=Br
M=Pd
X=I
M=Pt
X=Cl
M=Pd
X=I
M=Pt
X=Cl
M=Pt
X=I
ꢀ
6 exhibit intramolecular Sn···X
M (X=Cl, Br, I; M=Pd, Pt)
interactions ranging between
3.106(1) (Sn(2)····Cl(4), 1) and
3.408(1) ꢅ (Sn(1)···I(3), 5),
which are shorter than the sum
of the van der Waals radii of
the corresponding atoms. These
distances are the result of the
square-planar geometries of the
complexes rather than of bond-
ing interactions. This view is
supported by an atoms-in-mole-
cules (AIM) analysis performed
on the model compound cis-
ꢀ
Sn(1) C(1)
2.209
2.400
2.375
2.206
2.384
2.369
2.212
2.381
2.379
2.207
2.389
2.378
2.1255
2.155
2.165
ꢀ
Sn(1) O(1)
ꢀ
Sn(1) O(2)
ꢀ
Sn(1) N(1)
2.557
2.622
2.467
2.559
2.694
2.630
2.532
2.440
2.533
2.392
2.640
2.563
2.821
2.617
2.642
ꢀ
Sn(1) N(2)
ꢀ
Sn(1) Cl(1)
2.417
2.521
2.392
2.398
2.430
2.532
2.524
2.529
2.424
2.550
2.693
2.690
2.417
2.525
2.394
2.404
ꢀ
Sn(1) M(1)
ꢀ
M(1) X(3)
ꢀ
M(1) X(4)
Table 6. Calculated bond angles [8] for compounds 1–7 (BP86/def2-TZVP).
1
2
3
4
5
6
7
M=Pd
X=Cl
M=Pd
X=Br
M=Pd
X=I
M=Pt
X=Cl
M=Pd
X=I
M=Pt
X=Cl
M=Pt
X=I
[PtCl2ACTHNUTRGNEUNG(SnClH)2], which gave no
bond critical point for the
C(1)-Sn(1)-M(1)
C(1)-Sn(1)-Cl(1)
M(1)-Sn(1)-Cl(1)
O(1)-Sn(1)-O(2)
N(1)-Sn(1)-N(2)
Sn(1)-M(1)-Sn(2)
X(3)-M(1)-X(4)
131.3
95.4
133.2
159.5
132.8
97.6
129.5
157.4
134.5
96.4
129.2
157.3
129.7
98.0
132.2
159.4
141.0
97.0
121.7
138.5
102.1
119.1
136.5
101.4
121.9
ꢀ
Sn···Cl Pt interaction (see Fig-
ure S6 in the Supporting Infor-
mation).
146.2
104.0
97.1
146.0
106.5
93.8
145.6
180.0
180.0
100.6
103.5
101.0
96.7
99.2
95.4
100.6
103.5
The NBO analysis of cis-con-
figured compounds 1–6 re-
vealed that the O!Sn charge
transfer in compounds 1–4 is
Most interestingly, the Wiberg bond indices for the
Sn···Sn interactions in the cis-configured complexes 1–6,
which range between 0.09 (4) and 0.12 (5), show that these
are bonding interactions and contribute to the stabilisation
of the complexes. The corresponding MO that illustrates
this interaction for the platinum complex 4 is shown in
Figure 9. This is the HOMO-4 orbital, which can be descri-
bed as a three-centre bonding interaction of the dxy orbital
of the platinum atom with two formal sp2-hybridised orbitals
of the tin atoms (following the NBO theory). A more de-
tailed MO diagram is given in Figure S5 in the Supporting
Information.
twice as big as the N!Sn charge transfer in compounds 5
and 6 (Table 7). When analysing the hypothetical trans-con-
figured counterparts of complexes 1 and 4, it appeared that
the O,C,O-coordinating pincer-type ligands provide the
same charge-transfer stabilisation as in the cis-configured
complexes. This is in contrast to the behaviour of the N,C,N-
coordinating pincer-type ligands, which display a higher
donor strength in trans complexes than in the cis complexes
(Table 7). Furthermore, the NBO analysis indicates a natu-
ral charge at the tin atoms ranging from +1.45 (5) to +1.54
(4) and from ꢀ0.73 (5) to ꢀ0.40 (1) at the platinum or palla-
dium atoms, respectively. The NBO charges of the metal-
Table 7. Results of NBO calculations on complexes 1–7.
Compound[a]
Energy[b]
Sn···Sn
WBI[c]
Sn O/N
Sn
NBO
charge
M
NBO
charge
M Y
NBO
Sn X
NBO
Charge
ꢀ
Sn M
WBI[c]
ꢀ
ꢀ
ꢀ
[kcalmolꢀ1
]
WBI[c]
transfer
charge
charge
to Sn[d]
[kcalmolꢀ1
]
cis-[(R1SnCl)2PdCl2] (1)
cis-[(R1SnCl)2PdBr2] (2)
cis-[(R1SnCl)2PdI2] (3)
cis-[(R1SnCl)2PtCl2] (4)
cis-[(R2SnCl)2PdI2] (5)
cis-[(R2SnCl)2PtCl2] (6)
trans-[(R2SnI)2PtI2] (7)
ꢀ6.0
ꢀ5.8
ꢀ10.2
ꢀ10.5
2.1
0.107
0.105
0.106
0.092
0.119
0.104
0.077
0.65
0.64
0.62
0.72
0.63
0.68
0.70
0.19
0.19
0.19
0.23
0.16
0.18
0.16
+1.47
+1.47
+1.45
+1.54
+1.45
+1.45
+1.35
ꢀ0.40
ꢀ0.49
ꢀ0.64
ꢀ0.47
ꢀ0.73
ꢀ0.62
ꢀ1.06
ꢀ0.48
ꢀ0.42
ꢀ0.31
ꢀ0.50
ꢀ0.27
ꢀ0.41
ꢀ0.16
ꢀ0.49
ꢀ0.51
ꢀ0.51
ꢀ0.50
ꢀ0.58
ꢀ0.56
ꢀ0.39
50
50
50
60
24
26
46
0.5
3.2
[a] R1 =4-tBu-2,6-[P(O)
ACHTUNGTRENNUNG
(OiPr)2]2C6H2, R2 =2,6-(Me2NCH2)2C6H3. [b] Negative values indicate stabilisation of the cis over the trans isomer. [c] WBI=
Wiberg bond index. [d] Per O/N donor group.
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6703

R. Jambor, S. Herres-Pawlis, K. Jurkschat et al.
Conclusion
In this work we have shown that intramolecularly coordinat-
ed heteroleptic organostannylenes of the type RSnCl (R=4-
tBu-2,6-[P(O)ACHTNUGTRNE(UNG OiPr)2]2C6H2, 2,6-(Me2NCH2)2C6H3) behave
as s donors in PdII and PtII complexes and do not insert into
ꢀ
the corresponding M X bond. DFT calculations revealed
the intramolecular P=O!Sn coordination to be considera-
bly stronger than the N!Sn coordination and to favour the
cis-configured complexes over the trans compounds. For the
complexes containing the nitrogen-donor-stabilised organo-
stannylenes, the differences between the cis- and trans-con-
figured complexes are much smaller with the consequence
that both representatives (6, 7) could be isolated. The
N,C,N-coordinating pincer-type ligands are stronger donors
in the trans-configured complexes than in the cis-configured
complexes.
The Sn···Sn interactions in the cis-configured complexes
1–6, with distances shorter than twice the van der Waals
radius of the tin atom, are bonding interactions and contrib-
ute to the stability of the complexes. This is of fundamental
interest for understanding the chemical bonding in such
complexes. Finally, the family of tin–platinum complexes has
been extended by the first examples of complexes that con-
tain both s-bonded organostannylenes and trichloridostann-
yl ligands, with the latter originating from the insertion of
ꢀ
SnCl2 into the Pt Cl bond.
Experimental Section
General: All solvents were dried and purified by standard procedures.
All reactions were carried out under an atmosphere of dry nitrogen or
argon. The metal dihalides PtCl2, PdCl2 and PdI2 were purchased from
Figure 9. Top: Two degenerate HOMO-90/91 orbitals showing the two
Sigma–Aldrich. The organostannylenes 4-tBu-2,6-[P(O)ACHTUNGTERNN(UG OiPr)2]2C6H2SnX
ꢀ
Pt Sn bonds with high covalent character. Bottom: HOMO-4 orbital
showing the weak intramolecular Sn···Sn interaction.
(X=Cl, Br, I) and 2,6-(Me2NCH2)2C6H3SnCl were prepared according to
literature procedures.[51–53] Bruker DPX-300, DRX-400 and Bruker
Avance 500 spectrometers were used to record 1H, 13C, 31P, 119Sn and
195Pt NMR spectra. NMR chemical shifts (d) are given in ppm and are
referenced to Me4Si (1H, 13C), H3PO4 (85%, 31P), Me4Sn (119Sn) and 1.2m
bound halides and of the metals sum to approximately ꢀ1.5
to ꢀ1.3. This is due to the greater electronegativity of the
platinum and palladium atoms compared with tin and elec-
tron transfer from both tin-containing units. Formally, one
would expect a charge of ꢀ2 for the MX2 unit, but the NBO
charges represent not the formal charges but an impression
of the charge distribution.[66] This is consistent with the inter-
pretation of the Mçssbauer data, on the basis of which the
tin atoms were assigned the oxidation state III (in com-
pounds 3 and 4). In the trans-configured compound 7, the
situation is different due to a special delocalisation of the
Na2ACHTNUTGRNEUNG
[PtCl6] (195Pt). The NMR spectra were recorded at room temperature.
Mçssbauer spectra were recorded in constant-acceleration mode on a
home-made instrument designed and built by the Institut voor Kernen
Stralingsfysica (IKS), Leuven. The isomer shifts are referenced to a
source of Ca119mSnO3 from Amersham, UK, the samples being main-
tained at 90ꢁ2 K. The data were treated with a least-squares iterative
program, deconvoluting the spectrum into the sum of Lorentzians. IR
spectra were measured on a Nicolet 5PC device as KBr discs. ESI mass
spectra were recorded on a Thermoquest-Finnigan TSQ instrument with
acetonitrile as the mobile phase. UV/Vis spectra were recorded on an
Agilent Cary 60 UV/Vis spectrophotometer. The elemental analyses
were performed on a LECO-CHNS-932 analyser.
Computational details: The calculations were performed with Turbo-
mole[62] by using the BP86 pure functional[63] with the Ahlrichs def2-
TZVP basis set,[64] which includes effective core potentials on tin and
platinum. Tight conversion criteria were applied. Both stationary points
were characterised by frequency analysis and show the correct number of
negative eigenvalues (zero for a local minimum). Based on the geometry
obtained by the PB86/def2-TZVP method, a NBO analysis was per-
formed by using this method with NBO 5.0[66] as implemented in Gauss-
ꢀ ꢀ
Sn Pt Sn bonding interaction, which results in a more neg-
ative charge at the platinum (ꢀ1.1) and tin (+1.35) atoms. A
more detailed description will be the subject of further stud-
ies.
AHCTUNGTRENNUNG
ian 03.[67]
6704
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708

Organostannylene Palladium and Platinum Complexes
FULL PAPER
Synthesis of compounds 1–8, 10, and 11
(121.49 MHz, CD2Cl2): d=28.0 ppm (J
ACHUTNGTRENNUG(P,Sn)=26.7 Hz, JACHTUNGTREN(NGUN P,Sn)=191.7/
183.8 Hz); 119Sn{1H} NMR (111.92 MHz, CD2Cl2, 228C, Me4Sn): d=
cis-[(4-tBu-2,6-{P(O)
ACHTUNGTRENNUNG(OiPr)2}2C6H2SnCl)2PdCl2] (1): 4-tBu-2,6-[P(O)-
ꢀ257 ppm (t, J
ACHUTGTNRNEUG(N Sn,P)=192 Hz, JACHTUNGTERN(NUGN Sn,Sn)=6480 Hz); IR (KBr): n=2976,
ACHTUNGTRENNUNG
2932, 1384, 1177 (P=O), 1094, 999, 896, 848, 558 cmꢀ1; UV/Vis (CH2Cl2):
lmax =440 nm; elemental analysis calcd (%) for C44H78Cl2I2O12P4-
(0.29 g, 1.62 mmol) in toluene (5 mL). After the reaction mixture had
been stirred for 12 h, the solution was filtered and the toluene removed
in vacuo. Recrystallisation from benzene yielded 1.2 g (53%) of [(4-tBu-
AHCTUNGTERNPGNUN dSn2·2C7H8: C 39.23, H 5.34; found: C 38.7, H 5.1.
2,6-{P(O)ACHTUNGTRENNUNG(OiPr)2}2C6H2SnCl)2PdCl2]·C6H6 as yellow crystals that were
suitable for X-ray diffraction analysis. The crystals were dried in vacuo
for 2 h at 408C to remove the solvate.
M.p. 1538C (decomp.); 1H NMR (300.13 MHz, C6D6): d=8.04 (d, 3J-
The residue that had been filtered off was extracted with dichlorome-
thane. Addition of n-hexane to the extract gave compound 8 as deep-red
crystals that were suitable for X-ray diffraction analysis.
1
3
M.p. >2508C (decomp.); H NMR (300.13 MHz, CD2Cl2): d=8.02 (d, J-
(H,P)=14.3 Hz, 4H; Ar-H), 5.00 (m, 4H; CH), 4.75 (m, 4H; CH), 1.49
(d, 3J(H,H)=6.2 Hz, 12H; CHCH3), 1.41 (d, 3J
(H,H)=7.0 Hz, CHCH3),
1.40 (s, 18H; CCH3), 1.24 (d, 3J
(H,H)=6.2 Hz, 12H; CHCH3), 1.13 ppm
(d, 3J(H,H)=6.3 Hz, 12H; CHCH3); 31P{1H} NMR (121.49 MHz,
CD2Cl2): d=26.2 (J
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHUTNGREN(NUG P,Sn)=186 Hz, integral 3), 26.3 ppm (JACHTUNGTRENNUNG(P,Sn)=
193 Hz, integral 1); no reasonable 119Sn NMR spectrum was obtained; el-
emental analysis calcd (%) for C44H78Cl2I4O12P4Pd2Sn2: C 27.08, H 4.03;
found: C 26.8, H 4.0.
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
cis-[(4-tBu-2,6-{P(O)
CATHNUGTREN(NUNG OiPr)2}2C6H2SnCl)2PtCl2] (4): 4-tBu-2,6-[P(O)-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
PtCl2 (228 mg, 0.85 mmol) in toluene (5 mL). After the reaction mixture
had been stirred for 12 h, the solution was filtered. Recrystallisation from
toluene/hexanes yielded yellow crystals of 4·1.5C7H8 that were suitable
for X-ray diffraction analysis. After drying in vacuo for 2 h at 408C
663 mg (52%) of compound 4 were obtained.
;
UV/Vis (CH2Cl2): lmax =390 nm; elemental analysis calcd (%) for
C44H78Cl4O12P4PdSn2·C6H6 (1486.71):C 40.39, H 5.69; found: C 39.3, H
5.6.
cis-[(4-tBu-2,6-{P(O)
ACHTUNGTRENNUNG(OiPr)2}2C6H2SnCl)2PdBr2] (2): 4-tBu-2,6-[P(O)-
1
3
M.p. 1288C; H NMR (300.13 MHz, C6D6): d=8.04 (d, J
4H; Ar-H), 5.53–5.42 (m, 4H; CH), 4.87–4.73 (m, 4H; CH), 1.53 (d, 3J-
(H,H)=6.2 Hz, 12H; CH3), 1.19 (d, 3J
(H,H)=6.2 Hz, 12H; CH3), 1.15
(d, 3J(H,H)=6.2 Hz, 12H; CH3), 1.04 (s, 18H; tBu), 0.91 ppm (d, 3J-
(H,H)=6.2 Hz, 12H; CH3); 13C NMR (100.61 MHz, CD2Cl2): d=163.9
(t, 2J(C,P)=20.9 Hz; C-1), 154.6 (t, 3J(C,P)=12.1 Hz; C-4), 131.9 (dd, 2J-
(C,P)=4.9 Hz, 4J(C,P)=14.6 Hz; C-3/5), 131.5 (dd, 1J(13C,31P)=183.7 Hz,
3J
(C,P)=18.5 Hz; C-2/6), 74.8–74.6 (m; CH), 74.1–73.9 (m; CH), 35.6 (s;
(CH3)3), 31.4 (s; C(CH3)3), 24.5–24.4 (not resolved; CHCH3), 24.2–24.0
(not resolved; CHCH3), 23.8–23.7 ppm (not resolved; CHCH3);
31P{1H} NMR (121.49 MHz, CD2Cl2): d=27.5 ppm (J
(P,Sn)=126 Hz, J-
(P,Pt)=126 Hz); 119Sn{1H} NMR (111.92 MHz, CD2Cl2): d=ꢀ483 ppm (t,
(Sn,P)=130 Hz, (Sn,Sn)=1500 Hz,
(Sn,Pt)=28470 Hz); 195Pt NMR
(64.52 MHz, CD2Cl2): d=ꢀ4482 ppm (quint.,
(Pt,P)=122 Hz, 1J-
ACHTUNGTREN(NUNG H,P)=14.3 Hz,
ACHTUNGTRENNUNG
PdBr2 (144 mg, 0.54 mmol) in toluene (5 mL). After the reaction mixture
was stirred for 12 h, the solution was filtered. Crystallisation from tol-
uene/n-hexane yielded orange crystals that were suitable for X-ray dif-
fraction analysis. Recrystallisation from hexanes/CH2Cl2 in air and drying
in vacuo at 408C for 2 h gave 539 mg (66%) of [(4-tBu-2,6-{P(O)-
G
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
G
ACHTUNGTRENNUNG
T
R
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
C
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
J
N
J
G
JACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
JACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
AHCTUNGERTG(NNUN Pt,Sn)=28480/27190 Hz); IR (KBr): n=2981, 2935, 1467, 1386, 1180
ACHTUNGTRENNUNG
(P=O), 1004, 896, 850, 559 cmꢀ1; MS (+ESI): m/z: 1461 [MꢀClꢀ]+; ele-
mental analysis calcd (%) for C44H78Cl4O12P4PtSn2·C7H8: C 38.54, H 5.45;
found: C 38.2, H 5.3.
A
ACHTUNGTRENNUNG
(not resolved; CHCH3), 24.3–24.2 (not resolved; CHCH3), 24.1–24.0 (not
resolved; CHCH3), 23.9–23.8 ppm (not resolved; CHCH3); 31P{1H} NMR
cis-[2,6-(Me2NCH2)2C6H3SnCl]2PdI2
(5)
A
solution
of
2,6-
(121.49 MHz, CD2Cl2): d=27.7 ppm (JACHTUNTGRENNUG(P,Sn)=26.7 Hz, JCAHTUNGTREN(NNGU P,Sn)=181.6/
(Me2NCH2)2C6H3SnCl (187 mg, 0.54 mmol) in THF (40 mL) was stirred
with PdI2 (97 mg, 0,27 mmol) for 2 d. The resulting mixture was filtered
and the red solid residue was washed with hexane (2ꢆ10 mL) to give a
red solid of 5 (yield 227 mg, 80%).
174.9 Hz); 119Sn{1H} NMR (111.92 MHz, CD2Cl2): d=ꢀ321 ppm (t, J-
ACHTUNGTRENNUNG(Sn,P)=178 Hz, JACHTUNGTRENNUNG(Sn,Sn)=5640 Hz); IR (KBr): n=2977, 2930, 1384,
1177 (P=O), 1159 (P=O), 1120, 1094, 1000, 897, 558 cmꢀ1
(CH2Cl2): lmax =410 nm; elemental analysis calcd (%) for
C44H78Br2Cl2O12P4PdSn2·C7H8: C 38.53, H 5.45; found: C 38.1, H 5.1.
cis-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2PdI2] (3) and trans-[(4-tBu-2,6-
{P(O)(OiPr)2}2C6H2SnCl)PdI2]2 (8): 4-tBu-2,6-[P(O)(OiPr)2]2C6H2SnCl
; UV/Vis
1
M.p. 193–1958C. H NMR (500.13 MHz, CDCl3): d=2.70 (s, 6H; NCH3),
2.81 (s, 6H; NCH3), 3.95 (AB system, 2J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
(AB system, 2J
N
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
(1.0 g, 1.62 mmol) was added to a suspension of PdI2 (0.29 g, 0.81 mmol)
in toluene (5 mL). After the reaction mixture had been stirred for 12 h,
the solution was filtered. Crystallisation from toluene/n-hexane yielded
dark-red crystals that were suitable for X-ray diffraction analysis. Recrys-
tallisation from hexanes/CH2Cl2 in air and drying in vacuo at 408C for
2 h gave 442 mg (61%) of 3.
CDCl3): d=47.7 (NCH3), 48.7 (NCH3), 64.1 (NCH2), 125.7, 130.5, 142.2,
145.3 ppm; 119Sn{1H} NMR (186.49 MHz, CDCl3): d=ꢀ20 ppm (J-
ACHNUTTGRE(GUNNN Sn,Sn)=3885 Hz); elemental analysis calcd (%) for C24H40Cl2I2N4PdSn2
(1053.11): C 27.07, H 3.53; found: C 27.04, H 3.51.
cis-[2,6-(Me2NCH2)2C6H3SnCl]2PtCl2 (6): A solution of 2,6-(Me2NCH2)2-
M.p. 1708C (decomp.). 1H NMR (300.13 MHz, CD2Cl2): d=8.01 (d, 3J-
ACHTUNGTRENNUNG
AHCTUNGTRENGCNUN 6H3SnCl (393 mg, 1.10 mmol) and PtCl2 (151 mg, 0.55 mmol) in THF
(40 mL) was stirred for 3 d. The yellow solid residue was separated by fil-
tration and washed with hexane (2ꢆ10 mL) to give 489 mg (yield 90%)
of compound 6 as a yellow solid.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
M.p. 1998C (decomp.); 1H NMR (500.13 MHz, CDCl3): d=2.63 (s, 6H;
AHCTUNGTRENNUNG
NCH3), 2.87 (s, 6H; NCH3), 3.80 (AB system, 2J
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
CH2), 4.16 (AB system, 2J
N
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
N
ACHTUNGTRENNUNG
(not resolved; CHCH3), 24.3–24.2 (not resolved; CHCH3), 23.9–23.8 (not
resolved; CHCH3), 23.9–23.8 ppm (not resolved; CHCH3); 31P{1H} NMR
(125.77 MHz, CDCl3): d=47.2 (NCH3), 64.1 (NCH2), 125.6, 130.6, 142.9,
143.8 ppm; 119Sn{1H} NMR (186.49 MHz, CDCl3,): d=ꢀ254 ppm (1J-
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6705

R. Jambor, S. Herres-Pawlis, K. Jurkschat et al.
ACHTUNGTRENNUNG(Sn,Pt)=12640 Hz); elemental analysis calcd (%) for C24H40Cl4N4PtSn2
(958.90): C 29.76, H 3.90; found: C 29.73, H 3.87.
Acknowledgements
Financial support by the TU Dortmund (scholarship to M.W.), the Fonds
der Chemischen Industrie (fellowship to S.H.-P.) and the Bundesministe-
rium fꢁr Bildung und Forschung (MoSGrid, 01IG09006) is gratefully ac-
knowledged. Calculation time at the ARMINIUS Cluster at the PC2 Pa-
derborn and the SuGI Cluster at the Regionales Rechenzentrum Kçln
(RRZK) is gratefully acknowledged. Dr. Markus Schꢁrmann is gratefully
acknowledged for X-ray data acquisition. We also acknowledge the anon-
ymous reviewers for their valuable comments.
Synthesis of trans-[{2,6-(Me2NCH2)2C6H3}SnI]2PtI2 (7): A solution of 6
(0.40 g, 0.4 mmol) in CH2Cl2 (40 mL) to which had been added NaI
(0.25 g, 1.6 mmol) was stirred for 3 d. The resulting mixture was filtered
to remove NaCl and excess NaI. After the filtrate had been evaporated
to dryness, the solid residue thus obtained was washed with hexane (2ꢆ
10 mL) to give 0.36 g (68%) of complex 7 as a red solid.
M.p. 2358C (decomp.); 1H NMR (500.13 MHz, CDCl3): d=2.88 (s, 12H;
NCH3), 4.13 (s, 4H; CH2N), 7.29 (d, 3J
ACHTUNGTRENNUNG
7.46 ppm (t, 3J
ACHTUNGTRENNUNG
CDCl3): d=47.8 (NCH3), 64.7 (CH2N), 125.4, 130.3, 142.5, 147.5 ppm;
119Sn {1H} NMR (186.49 MHz, CDCl3): d=ꢀ80 ppm; elemental analysis
calcd (%) for C24H40I4N4PtSn2 (1324.70): C, 21.76, H 3.06; found: C,
21.73, H 3.03.
[1] M. Veith, O. Recktenwald, Topics Curr. Chem. 1982, 104, 1–55.
[2] For selected reviews, see: a) W. Petz, Chem. Rev. 1986, 86, 1019–
1047; b) M. S. Holt, W. L. Wilson, J. H. Nelson, Chem. Rev. 1989, 89,
11–49; c) M. F. Lappert, R. S. Rowe, Coord. Chem. Rev. 1990, 100,
267–292; d) D. Agustin, M. Ehses, C. R. Chim. 2009, 12, 1189–1227;
e) H. K. Sharma, I. Haiduc, K. H. Pannell in The Chemistry of Or-
ganic Germanium, Tin and Lead Compounds, Vol. 2 (ed. Z. Rappo-
port), John Wiley & Sons, Ltd, Chichester, 2003; f) I. Saur, S. G.
Alonso, J. Barrau, Appl. Organomet. Chem. 2005, 19, 414–428.
[3] P. J. Davidson, M. F. Lappert, J. Chem. Soc. Chem. Commun. 1973,
317a–317a.
[4] J. D. Cotton, P. J. Davison, D. E. Goldberg, M. F. Lappert, K. M.
Thomas, J. Chem. Soc. Chem. Commun. 1974, 893–895.
[5] D. E. Goldberg, D. H. Harris, K. M. Thomas, M. F. Lappert, J.
Chem. Soc. Chem. Commun. 1976, 261–262.
[6] P. B. Hitchcock, M. F. Lappert, S. A. Thomas, A. J. Thorne, A. J.
Carty, N. J. Taylor, J. Organomet. Chem. 1986, 315, 27–44.
[7] K. Angermund, K. Jonas, C. Krꢁger, J. L. Latten, Y.-H. Tsay, J. Or-
ganomet. Chem. 1988, 353, 17–25.
[8] M. Veith, L. Stahl, V. Huch, Inorg. Chem. 1989, 28, 3278–3280.
[9] M. Veith, L. Stahl, V. Huch, J. Chem. Soc. Chem. Commun. 1990,
359–361.
[10] C. Pluta, K. R. Pçrschke, R. Mynott, P. Betz, C. Krꢁger, Chem. Ber.
1991, 124, 1321–1325.
[11] R. M. Whittal, G. Ferguson, J. F. Gallagher, W. E. Piers, J. Am.
Chem. Soc. 1991, 113, 9867–9868.
[12] W. E. Piers, R. M. Whittal, G. Ferguson, J. F. Gallagher, R. D. J.
Froese, H. J. Stronks, P. H. Krygsman, Organometallics 1992, 11,
4015–4022.
[13] S. L. Ellis, P. B. Hitchcock, S. A. Holmes, M. F. Lappert, MJ. Slade,
J. Organomet. Chem. 1993, 444, 95–99.
[14] M. Weidenbruch, A. Stilter, K. Peters, H. G. von Schnering, Z.
Anorg. Allg. Chem. 1996, 622, 534–538.
[15] J. J. Schneider, J. Hagen, D. Blꢂser, R. Boese, C. Krꢁger, Angew.
Chem. 1997, 109, 771–773; Angew. Chem. Int. Ed. Eng. 1997, 36,
739–741.
[16] M. Weidenbruch, A. Stilter, W. Saak, K. Peters, H. G. von Schner-
ing, J. Organomet. Chem. 1998, 560, 125–129.
[17] J. J. Schneider, N. Czap, D. Blꢂser, R. Boese, J. Organomet. Chem.
1999, 584, 338–343.
[18] J. J. Schneider, N. Czap, D. Blꢂser, R. Boese, J. Am. Chem. Soc.
1999, 121, 1409–1410.
[19] J. J. Schneider, J. Hagen, D. Blꢂser, R. Boese, F. F. de Biani, P. Za-
nello, C. Krꢁger, Eur. J. Inorg. Chem. 1999, 1987–1993.
[20] J. Klett, K. W. Klinkhammer, M. Niemeyer, Chem. Eur. J. 1999, 5,
2531–2536.
[21] J. J. Schneider, J. Hagen, D. Spickermann, D. Blꢂser, R. Boese, F. F.
de Biani, F. Laschi, P. Zanello, Chem. Eur. J. 2000, 6, 237–246.
[22] J. J. Schneider, N. Czap, D. Blꢂser, R. Boese, J. Ensling, P. Gꢁtlich,
C. Janiak, Chem. Eur. J. 2000, 6, 468–474.
Isolation of [(4-tBu-2,6-{P(O)
ACHUTGTNRNEGU(N OiPr)2}2C6H2SnCl)2PtACHTUGNTERN(NUGN SnCl3)2]·2C7H8 (10):
4-tBu-2,6-[P(O)(OiPr)2]2C6H2SnCl (1.18 g, 1.92 mmol) was added to a
ACHTUNGTRENNUNG
suspension of PtCl2 (0.17 g, 0.39 mmol) and SnCl2 (0.24 g, 0.79 mmol) in
toluene (5 mL). After the reaction mixture had been stirred for 12 h, the
solution was filtered. Recrystallisation from toluene/n-hexane yielded red
crystals (m.p. 1858C (decomp.)) suitable for X-ray diffraction analysis.
There was not enough material to perform an elemental analysis.
Isolation
·C7H8·0.5C6H14
of
[(4-tBu-2,6-{P(O)
(11): 4-tBu-2,6-[P(O)ACHTUGNTRENNNUG
G
ACHTUNGTRENNUNG
H
1.62 mmol) was added to a suspension of PtCl2 (0.11 g, 0.41 mmol) in the
presence of traces of SnCl2 in toluene (5 mL). After the reaction mixture
had been stirred for 12 h, the solution was filtered. Recrystallisation from
toluene/n-hexane yielded a few red single crystals (m.p. 1338C) suitable
for X-ray diffraction analysis. Elemental analysis calcd (%) for
C76H133Cl8O19P6PtSn5 (2608.96): C 34.99, H 5.14; found: C 35.0, H 4.7
(the crystals used for X-ray diffraction and elemental analyses contained
one less Cl, replaced by one OH).
X-ray crystallography: Intensity data for the crystals 1·C6H6, 2·C7H8,
4·1.5C7H8, 5, 6, 7·2CHCl3 and 11·C7H8·0.5C6H14 were collected on a
Nonius KappaCCD diffractometer (Bruker) and for the crystals 3·C7H8,
8 and 10·2C7H8 on an XcaliburS CCD diffractometer (Oxford Diffrac-
tion) using MoKa radiation at 110 K. The structures were solved by direct
methods (Sir92)[68] for 7·2CHCl3 and for the remaining structures
SHELXS-97[69] was used. Refinements were carried out against F2 by
using SHELXL-97.[69]. C H hydrogen atoms were positioned in idealised
ꢀ
geometries and refined by using a riding model. All non-hydrogen atoms
were refined by using anisotropic displacement parameters except for dis-
ordered carbon atoms in compound 4·1.5C7H8, all methyl groups in com-
pound 8, and C1 to C10 in compound 10·2C7H8 to benefit the data/pa-
rameter ratio. For compound 10·2C7H8, twin refinement was carried out
with a final BASF value of 0.508. At least two isopropyl groups and
sometimes one tert-butyl group in compounds 1·C6H6, 2·C7H8, 4·1.5C7H8,
8, 10·2C7H8 and 11·C7H8·0.5C6H14 are affected by disorder and refined by
a split model over two positions with occupancies of between 70:30 and
50:50. For more details, see the Supporting Information. In compound
4·1.5C7H8, one pincer-type ligand backbone (C13–C20) is disordered and
split into two positions with equal occupancies (see Figure S7 in the Sup-
porting Information). In compound 11·C7H8·0.5C6H14, the chlorine atoms
Cl1 and Cl3 share their positions with hydroxy groups O1H and O3H
(we were not able to localise the hydrogen atoms in the difference Fouri-
er map). Their occupancies were allowed to refine freely until a constant
number was obtained and rounded down to the integer values 50:50 to
simplify the sum formula. The severely disordered and non-coordinating
solvents of compounds 3·C7H8 and 11·C7H8·0.5C6H14 were removed by
Platon/SQUEEZE[61] to improve the main part of their structures. Fig-
ures 1–8 were created by using Diamond 3..
[23] P. Braunstein, M. Veith, J. Blin, V. Huch, Organometallics 2001, 20,
627–633.
[24] B. E. Eichler, A. D. Phillips, S. T. Haubrich, B. V. Mork, P. P. Power,
Organometallics 2002, 21, 5622–5627.
[25] G. W. Bushnell, D. T. Eadie, A. Pidcock, A. R. Sam, R. D. Holmes-
Smith, S. R. Stobart, E. T. Brennan, T. S. Cameron, J. Am. Chem.
Soc. 1982, 104, 5837–5839.
CCDC-887667 (1·C6H6), -887668 (2·C7H8), -887669 (3·C7H8), -887670
(4·1.5C7H8), -887671 (5), -887672 (6), -795540 (7·2CHCl3), -887673 (8),
-887674 (10·2C7H8) and -887675 (11·C7H8·0.5C6H14), contain the supple-
mentary 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.
6706
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708

Organostannylene Palladium and Platinum Complexes
FULL PAPER
[26] J. F. Almeida, K. R. Dixon, C. Eaborn, P. B. Hitchcock, A. Pidcock,
J. Vinaixa, J. Chem. Soc. Chem. Commun. 1982, 1315–1316.
[27] M. F. Lappert, P. P. Power, J. Chem. Soc., Dalton Trans. 1985, 51–57.
[28] P. B. Hitchcock, M. F. Lappert, M. C. Misra, J. Chem. Soc. Chem.
Commun. 1985, 863–864.
[29] G. K. Campbell, P. B. Hitchcock, M. F. Lappert, M. C. Misra, J. Or-
ganomet. Chem. 1985, 289, C1–C4.
[30] T. A. K. Al-Allaf, C. Eaborn, P. B. Hitchcock, M. F. Lappert, A. Pid-
cock, J. Chem. Soc. Chem. Commun. 1985, 548–550.
[31] V. V. Bashilov, V. I. Sokolov, Yu. L. Slovokhotov, Yu. T. Struchkov,
J. Organomet. Chem. 1987, 327, 285–293.
[32] R. Usꢇn, J. Forniꢃs, M. Tomꢀs, I. Usꢇn, Angew. Chem. 1990, 102,
1518–1519; Angew. Chem. Int. Ed. Engl. 1990, 29, 1449–1450.
[33] J. Krause, C. Pluta, K.-R. Pçrschke, R. Goddard, J. Chem. Soc.
Chem. Commun. 1993, 1254–1256.
Pçttgen, L. Wesemann, Angew. Chem. 2008, 120, 977–980; Angew.
Chem. Int. Ed. 2008, 47, 963–966; j) S. Hagen, H. Schubert, C.
Maichle-Mossmer, I. Pantenburg, F. Weigend, L. Wesemann, Inorg.
Chem. 2007, 46, 6775–6784; k) T. Gꢂdt, K. Eichele, L. Wesemann,
Organometallics 2006, 25, 3904–3911; l) B. M. Day, P. W. Dyer, M. P.
Coles, Dalton Trans. 2012, 41, 7457–7460.
[46] a) A. Albinati, R. Nꢂgeli, H. Rꢁegger, P. S. Pregosin, Angew. Chem.
1982, 94, 310–311; Angew. Chem. Int. Ed. Engl. 1982, 21, 284–285;
b) A. Albinati, P. S. Pregosin, H. Rꢁegger, Angew. Chem. 1984, 96,
63–63; Angew. Chem. Int. Ed. Engl. 1984, 23, 78–79; c) M. Grassi,
S. V. Meille, A. Musco, R. Pontellini, A. Sironi, J. Chem. Soc. Dalton
Trans. 1990, 251–255; d) E. Brivio, A. Ceriotti, L. Garlaschelli, M.
Manassero, M. Sansoni, J. Chem. Soc. Chem. Commun. 1995, 2055–
2056.
[47] W. M. Teles, N. L. Speziali, C. A. L. Filgueiras, Polyhedron 2000, 19,
739–742.
[34] F. Schager, K. Seevogel, K.-R. Pçrschke, M. Kessler, C. Krꢁger, J.
Am. Chem. Soc. 1996, 118, 13075–13076.
ˇ
[48] a) B. Kasnꢀ, R. Jambor, M. Schꢁrmann, K. Jurkschat, J. Organomet.
ˇ
[35] J. Krause, K.-J. Haack, K.-R. Pçrschke, B. Gabor, R. Goddard, C.
Pluta, K. Seevogel, J. Am. Chem. Soc. 1996, 118, 804–821.
[36] M. Veith, A. Mꢁller, L. Stahl, M. Nçtzel, M. Jarczyk, V. Huch,
Inorg. Chem. 1996, 35, 3848–3855.
Chem. 2008, 693, 3446–3450; b) R. Jambor, B. Kasnꢀ, S. G. Koller,
C. Strohmann, M. Schꢁrmann, K. Jurkschat, Eur. J. Inorg. Chem.
2010, 6, 902–908; c) R. Dostꢀlova, L. Dostꢀl, A. Ruzicka, R.
Jambor, Organometallics 2011, 30, 2405–2410; d) J. Martincovꢀ, R.
˚
ˇ
ˇ
˚ ˇ ˇ
[37] T. A. K. Al-Allaf, J. Chem. Res. 2003, 101–104.
Dostꢀlovꢀ, L. Dostꢀl, A. Ruzicka, R. Jambor, Organometallics 2009,
[38] Z. Bꢃni, R. Scopelliti, R. Roulet, Inorg. Chem. Commun. 2005, 8,
99–101.
28, 4823–4828; e) J. Martincovꢀ, R. Jambor, M. Schꢁrmann, K. Ju-
ˇ
rkschat, J. Honzꢈcek, F. A. Almeida Paz, Organometallics 2009, 28,
[39] a) I. Schwager, J. F. Knifton (Texaco Development Corp.),
DE2322751, 1973; C.-Y. Hsu, M. Orchin, J. Am. Chem. Soc. 1975,
97, 3553–3553; b) I. Schwager, J. F. Knifton, J. Catal. 1976, 45, 256–
257; for recent exemples, see: c) R. van Duren, J. I. van der Vlugt,
H. Kooijman, A. L. Spek, D. Vogt, Dalton Trans. 2007, 1053–1059;
d) E. Robꢃ, C. Hegedus, J. Bakos, Y. Coppel, J.-C. Daran, M. Gouy-
gou, Inorg. Chim. Acta 2008, 361, 1861–1867; e) G. Petocz, G. Ran-
gits, M. Shaw, H. de Bod, D. B. G. Williams, L. Kollar, J. Organomet.
Chem. 2009, 694, 219–222.
[40] a) R. D. Cramer, E. L. Jenner, R. V. Lindsey Jr. , U. G. Stolberg, J.
Am. Chem. Soc. 1963, 85, 1691–1692; b) L. P. Van’t Hof, B. G.
Linsen, J. Catal. 1967, 7, 295–297; c) D. H. Goldsworthy, F. R. Hart-
ley, S. G. Murray, J. Mol. Catal. 1983, 19, 269–276; d) J. C. Bailar Jr.
, H. Itatani, J. Am. Chem. Soc. 1967, 89, 1592–1599; e) J. C. Bai-
lar Jr. , H. Itatani, Inorg. Chem. 1965, 4, 1618–1620; f) K. Kushi, H.
Kanai, K. Tamara, S. Yoshida, Chem. Lett. 1972, 1, 539–542; hydro-
genation also occurs as a side-reaction in hydroformylation, see:
g) S. C. Tang, L. Kim, J. Mol. Catal. 1982, 14, 231–240; h) I. Tꢇth,
C. J. Elsevier, J. G. de Vries, J. Bakos, W. J. J. Smeets, A. L. Spek, J.
Organomet. Chem. 1997, 540, 15–25; i) J. I. van der Vlugt, R. van
Duren, G. D. Batema, R. den Heeten, A. Meetsma, J. Fraanje, K.
Goubitz, P. C. J. Kamer, P. W. N. M. van Leeuwen, D. Vogt, Organo-
metallics 2005, 24, 5377–5382.
4778–4782; f) V. Deꢀky, M. Schꢁrmann, K. Jurkschat, Z. Anorg.
Allg. Chem. 2009, 635, 1380–1383; g) J. Martincovꢀ, L. Dostꢀl, A.
˚
ˇ
ˇ
Ruzicka, J. Taraba, R. Jambor, Organometallics 2007, 26, 4102;
h) M. Wagner, K. Dorogov, M. Schꢁrmann, K. Jurkschat, Dalton
Trans. 2011, 40, 8839–8848.
[49] a) Y. Cabon, H. Kleijn, A. M. Siegler, A. L. Spek, R. J. M. Klein
Gebbink, B. J. Deelman, Dalton Trans. 2010, 39, 2423–2427; b) Y.
Cabon, I. Reboule, M. Lutz, R. J. M. Klein Gebbink, B.-J. Deelman,
Organometallics 2010, 29, 5904–5911; c) J. Wagler, A. F. Hill, T.
Heine, Eur. J. Inorg. Chem. 2008, 4225–4229; d) J. Wagler, E. Bren-
dler, Angew. Chem. 2010, 122, 634–637; Angew. Chem. Int. Ed.
2010, 49, 624–627; e) E. Brendler, E. Wachtler, T. Heine, L. Zhech-
kov, T. Langer, R. Pçttgen, A. F. Hill, J. Wagler, Angew. Chem.
2011, 123, 4793–4797; Angew. Chem. Int. Ed. 2011, 50, 4696–4700.
[50] a) P. Pyykkç, M. Atsumi, Chem. Eur. J. 2009, 15, 186–197; b) P.
Pyykkç, M. Atsumi, Chem. Eur. J. 2009, 15, 12770–12779.
[51] M. Henn, V. Deꢀky, S. Krabbe, M. Schꢁrmann, M. H. Prosenc, S.
Herres-Pawlis, B. Mahieu, K. Jurkschat, Z. Anorg. Allg. Chem. 2011,
637, 211–223.
[52] M. Mehring, C. Lçw, M. Schꢁrmann, F. Uhlig, K. Jurkschat, B.
Mahieu, Organometallics 2000, 19, 4613–4623.
[53] J. T. B. H. Jastrzebski, P. A. van der Schaaf, J. Boersma, G. van Ko-
ten, M. C. Zoutberg, D. Heijdenrijk, Organometallics 1989, 8, 1373–
1375.
[54] J. E. Huheey, E. A. Keiter, R. L. Keiter, Anorganische Chemie:
Prinzipien von Struktur und Reaktivitꢀt, Walter de Gruyter, Berlin
New York, 1995, p. 335.
[41] H. A. Tayim, J. C. Bailar, Jr. J. Am. Chem. Soc. 1967, 89, 3420–3424.
[42] a) I. G. Jung, J. Seo, S. I. Lee, S. Y. Choi, Y. K. Chung, Organometal-
lics 2006, 25, 4240–4242; b) H. Lee, M.-S. Jang, J.-T. Hong, H.-Y.
Jang, Tetrahedron Lett. 2008, 49, 5785–5788.
[43] G. K. Anderson, H. C. Clark, J. A. Davies, Organometallics 1982, 1,
64–70.
[55] J. D. Cotton, P. J. Davidson, M. F. Lappert, J. D. Donaldson, J. Silver,
J. Chem. Soc. Dalton Trans. 1976, 2286–2290.
[44] a) J. H. Nelson, N. W. Alcock, Inorg. Chem. 1982, 21, 1196–1200;
b) B. Z. Momeni, M. A. Amini, T. Pape, S. W. Ng, F. E. Hahn, J.
Mol. Struct. 2004, 697, 97–100; c) B. Z. Momeni, L. J. Baleh, S.
Hamzeh, F. Rominger, J. Coord. Chem. 2007, 60, 285–293; d) M.
[56] J. G. Stevens, V. E. Stevens, Mçssbauer effect data index, Plenum
Press, New York, 1972, p. 23.
[57] The 31P and 119Sn NMR spectra of complex 2, even after several re-
crystallisations, show additional low-intensity resonances [dP =26.3,
27.6, 27.7 ppm, dSn =ꢀ332 ppm (complex pattern)].
ˇ
Melnꢈk, P. Mikus, Main Group Met. Chem. 2012, 35, 117–127.
[45] a) T. Marx, B. Mosel, I. Pantenburg, S. Hagen, H. Schulze, L. Wese-
mann, Chem. Eur. J. 2003, 9, 4472–4478; b) A. V. Zabula, T. Pape,
A. Hepp, F. E. Hahn, Dalton Trans. 2008, 5886–5890; c) M. Kilian,
H. Wadepohl, L. H. Gade, Eur. J. Inorg. Chem. 2008, 1892–1900;
d) M. Kilian, H. Wadepohl, L. H. Gade, Organometallics 2008, 27,
524–533; e) M. Kilian, H. Wadepohl, L. H. Gade, Dalton Trans.
2008, 582–584; f) M. Kilian, H. Wadepohl, L. H. Gade, Organome-
tallics 2007, 26, 3076–3078; g) M. Kirchmann, S. Fleischhauer, L.
Wesemann, Organometallics 2008, 27, 2803–2808; h) M. Kirchmann,
T. Gadt, K. Eichele, L. Wesemann, Eur. J. Inorg. Chem. 2008, 2008,
2261–2265; i) M. Kirchmann, K. Eichele, F. M. Schappacher, R.
[58] M. Henn, Dissertation, TU Dortmund, 2003; Neue intramolekular
koordinierte Organoelementverbindungen des Zinns und des Anti-
mons unter Verwendung O,C,O-koordinierender ZangenACHTUNGTRENNUNGliACHTUNGTRENNUNGganACHTUNGTRENNUNGden,
Shaker, Aachen, 2005.
[59] R. Jambor, S. Herres-Pawlis, M. Schꢁrmann, K. Jurkschat, Eur. J.
Inorg. Chem. 2011, 2011, 344–348.
[60] A. R. Rossi, R. Hoffmann, Inorg. Chem. 1975, 14, 365–374.
[61] A. L. Spek, Acta Crystallogr. 2009, D65, 148–155.
[62] TURBOMOLE V5–7–1, 2004, University of Karlsruhe.
[63] a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648–5652; b) J. P. Perdew,
Phys. Rev. B 1986, 33, 8822–8824.
Chem. Eur. J. 2013, 19, 6695 – 6708
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6707

R. Jambor, S. Herres-Pawlis, K. Jurkschat et al.
[64] F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297–
Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J.
Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar,
J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A.
Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, ꢉ.
Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian,
Inc., Wallingford CT, 2004.
3305.
˚
ˇ
ˇ
[65] a) J. Martincovꢀ, L. Dostꢀl, S. Herres-Pawlis, A. Ruzicka, R.
Jambor, Chem. Eur. J. 2011, 17, 7423–7427; b) M. Bouska, L.
˘
ˇ
Dostꢀl, Z. Padelkovꢀ, A. Lycka, S. Herres-Pawlis, K. Jurkschat, R.
Jambor, Angew. Chem. 2012, 124, 3535–3540; Angew. Chem. Int.
˚
ˇ
ˇ
Ed. 2012, 51, 3478–3482; c) J. Martincovꢀ, L. Dostꢀl, A. Ruzicka, S.
Herres-Pawlis, R. Jambor, Z. Anorg. Allg. Chem. 2012, 638, 1672–
1675.
[66] F. Weinhold, C. Landis, Valency and Bonding: A Natural Bond Orbi-
tal Donor-Acceptor Perspective, Cambridge University Press, New
York, 2005.
[67] Gaussian 03, Revision E.01, M. J. Frisch, G. W. Trucks, H. B. Schle-
gel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V.
Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X.
Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Son-
nenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven,
J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J.
[68] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J. Appl.
Crystallogr. 1993, 26, 343–350.
[69] G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112–122.
[70] Diamond - Crystal and Molecular Structure Visualization, Version
3.2i, 2012, Crystal Impact - Dr. H. Putz & Dr. K. Brandenburg
GbR, Kreuzherrenstr. 102, 53227 Bonn, Germany, http://www.crys
talimpact.com/diamond
Received: October 2, 2012
Revised: January 31, 2013
Published online: March 27, 2013
6708
www.chemeurj.org
ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 6695 – 6708