Synthesis and characterization of perhalophenyltin derivatives. Study of their reactivity toward phosphine gold(I) chlorides

Article abstract of DOI:10.1016/j.jorganchem.2010.07.019

The (perhalophenyl)tin derivatives [SnR₄] (1-3) and [SnR ₃Cl] (4-6) (R = C₆F₅, C₆F ₃Cl₂, C₆Cl₅) were prepared from SnCl₄ and LiR or [SnR₄] in the appropriate molar ratio, while the dinuclear complexes [SnR₃]₂ (7-9) were obtained by treatment of [SnR₃Cl] with potassium under toluene reflux. Complexes 2, 6·0.5toluene and 7 were structurally characterized, the latter displaying a Sn-Sn bond of 2.808(7) , which indicates a strong tin-tin bond with covalent character in solid state. The hexaaryldistannanes 7-9 undergo transmetallation reactions with gold(I) derivatives, such as [AuCl(PPh ₃)] or [(AuCl)₂(μ-dppm)], affording the neutral species [AuR(PPh₃)] (10-12) or [(AuR)₂(μ-dppm)] (13-15) or the ionic product [Au₃Cl₂(μ-dppm)₂][Sn(C ₆F₅)₃Cl₂] (16). The crystal structures of 14·CH₂Cl₂, 15 and 16·2CH ₂Cl₂ were determined by X-ray diffraction, the latter showing a Au₃ nearly equilateral triangular core in the cation with gold-gold contacts of 3.128(7) and 3.227(12) . The main difference between the molecular structures of 14·CH₂Cl₂ and 15 (both of them displaying intramolecular gold-gold contacts of 3.142(6) and 3.160(4) , respectively) is the presence of an intermolecular Au?Au interaction of 3.2126(8) in the case of the C₆F₃Cl₂ complex that gives rise to a tetranuclear unit.

Full text of DOI:10.1016/j.jorganchem.2010.07.019

Journal of Organometallic Chemistry 695 (2010) 2385e2393
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and characterization of perhalophenyltin derivatives. Study of their
reactivity toward phosphine gold(I) chlorides
*
R. Vilma Bojan, José M. López-de-Luzuriaga , Miguel Monge, M. Elena Olmos
Departamento de Química, Universidad de la Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC, Complejo Científico Tecnológico, 26006 Logroño, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
The (perhalophenyl)tin derivatives [SnR4] (1e3) and [SnR3Cl] (4e6) (R ¼ C6F5, C6F3Cl2, C6Cl5) were
prepared from SnCl4 and LiR or [SnR4] in the appropriate molar ratio, while the dinuclear complexes
[SnR3]2 (7e9) were obtained by treatment of [SnR3Cl] with potassium under toluene reflux. Complexes 2,
6$0.5toluene and 7 were structurally characterized, the latter displaying a SneSn bond of 2.808(7) Å,
which indicates a strong tinetin bond with covalent character in solid state. The hexaaryldistannanes
Received 24 June 2010
Received in revised form
13 July 2010
Accepted 15 July 2010
Available online 23 July 2010
7e9 undergo transmetallation reactions with gold(I) derivatives, such as [AuCl(PPh3)] or [(AuCl)2(
dppm)], affording the neutral species [AuR(PPh3)] (10e12) or [(AuR)2( -dppm)] (13e15) or the ionic
product [Au3Cl2( -dppm)2][Sn(C6F5)3Cl2] (16). The crystal structures of 14$CH2Cl2, 15 and 16$2CH2Cl2
m-
m
Keywords:
m
Perhalophenyl groups
Lewis acidity
Tinetin single bond
Gold
were determined by X-ray diffraction, the latter showing a Au3 nearly equilateral triangular core in the
cation with goldegold contacts of 3.128(7) and 3.227(12) Å. The main difference between the molecular
structures of 14$CH2Cl2 and 15 (both of them displaying intramolecular goldegold contacts of 3.142(6)
and 3.160(4) Å, respectively) is the presence of an intermolecular Au/Au interaction of 3.2126(8) Å in the
case of the C6F3Cl2 complex that gives rise to a tetranuclear unit.
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
On the other hand, compounds with goldetin interactions have
been prepared through acidebase reactions between phosphine-
Perhalophenyl groups C6X5 (X ¼ F, Cl) have been widely used in
the preparation of stable organotransition metal compounds [1],
and also provide an enhancement of the Lewis acidity in main group
derivatives [2], making the later ones effective catalysts in organic
synthesis [2,3]. Among the organotin derivatives, only those with
pentafluorophenyl groups were synthesized and studied, i.e. the
structurally characterized tetrakis(pentafluorophenyl)tin [4]
showed no catalytic activity in Mukaiyama-aldol reaction of
ketene silyl acetal, while replacement of one or two C6F5 groups by
halides (bromine or chlorine) considerably improved its activity [3].
Although [SnR3]2 (R ¼ alkyl, aryl or other organic moiety) are well
known compounds [5e9], and give versatile reactions with cleavage
of the SneSn single bond by chemical oxidation [10e12], insertion
[13], addition [14], and cross-coupling reactions with aryl halides
[10,15], hexaorganodistannanes with perhalophenyl groups have not
been studied yet. Both the chemical oxidation and the cross-coupling
reaction afford the corresponding triorganotin halide, but in the latter
process the heteroleptic tetraorganotin derivative, which is further
used i.e. in fluorous labelling strategy [16], is also obtained.
gold(I) electrophiles and tin nucleophiles, such as SnCl2 or
[SnB11H11
]
2ꢀ [17e20]. In the last years, our group is focused in the
synthesis and study of the properties of complexes with metale
metal interactions, also usually employing an acidebase synthetic
strategy. Thus, we were interested in the synthesis of perhalophe-
nyltin compounds, which would presumably present a higher Lewis
acidic tin centre than in complexes with different organic substitu-
ents, and that, in principle, may behave as strong Lewis acids versus
d10 transition metal compounds, resulting in the formation of
species with metallophilic interactions. Thus, we prepared the
organotinderivatives [SnR4] (1e3), [SnR3Cl](4e6) and[SnR3]2 (7e9)
(R ¼ C6F5, C6F3Cl2, C6Cl5) and studied their reactivity against [AuCl
(PPh3)] or [(AuCl)2(
only some of them react and undergo transmetallation reactions,
affording the neutral species [AuR(PPh3)] (10e12) or [(AuR)2(
m-dppm)]. In contrast with what was expected,
m-
dppm)] (13e15) or the ionic [Au3Cl2(
m-dppm)2][Sn(C6F5)3Cl2] (16).
2. Results and discussion
2.1. Synthesis and characterization
[Sn(C6F5)4] (1) was prepared, according to the method described
in the literature [4], by reaction of tin tetrachloride with LiC6F5 (1:4)
* Corresponding author. Tel.: þ34 941299649; fax: þ34 941299621.
E-mail address: josemaria.lopez@unirioja.es (J.M. López-de-Luzuriaga).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.07.019

2386
R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
in diethyl ether at low temperature. The dichlorotrifluorophenyl
and pentachlorophenyl related products (2, 3) were prepared in the
similar manner by the reaction between the corresponding LiR and
SnCl4 using Schlenk techniques (Eq. (1)). They were obtained as
white (2) or pale yellow (3) solids soluble in toluene and partially
soluble in chlorinated solvents and hexane, and their analytical and
spectroscopic data agree with the proposed formulation.
para and meta fluorine atoms, respectively, indicating the
equivalence of the aryl groups in the molecule. In the case of
complex 5, the resonances of the fluorine atoms of the C6F3Cl2
groups appear at ꢀ95.9 (Fo) and ꢀ101.7 ppm (Fp) (2:1), which
indicates an up-field shift for the singlet of the para fluorine
atoms if compared with the spectrum of 2, due to the presence of
the chlorine atom in 5.
We have observed in our compounds that their mass spectra
often show species formed by the loss of the halogen atom. Both the
Et2O=ꢀ60 ꢁC=1 h
4LiR þ SnCl4
½SnR4ꢂ þ 4LiCl
ꢃ
MALDI(ꢀ) mass spectra of 4 and 5 show the ion [M ꢀ Cl]ꢀ at m/
R ¼ C6F5ð1Þ; C6F3Cl2ð2Þ; C6Cl5ð3Þ
(1)
z ¼ 621 and 719, respectively, as the base peak. Besides, peaks due
The 19F NMR spectrum of complex 2 shows two singlets located
at ꢀ95.7 (Fo) and ꢀ104.4 ppm (Fp), instead of the singlet at
ꢀ112.6 ppm that is observed in the 19F NMR spectrum of the free
C6F3Cl3, indicating that the C6F3Cl2 groups are equivalent and
bonded to the tin(IV) centre.
ꢃ
to the formation of the fragments [M ꢀ Cl]ꢀ (m/z ¼ 866, 50%) and
ꢃ
[M-C6Cl5]ꢀ (m/z ¼ 653, 15%) were detected in the MALDI(ꢀ) mass
spectrum of 6.
Distannanes are formed in a great variety of reactions, and they
can sometimes be isolated as by-products [10], but till date no
derivatives with perhalophenyl groups had been described. One
would expect that this type of complexes could be difficult to
prepare because of the ease of cleavage of the tinetin bond, even
more considering that in the related germanium complex [Ge
(C6F5)3]2 the GeeGe can be broken more easily than in other
hexaorgano-digermane derivatives [23]. In contrast, the three
hexaorganodistannanes [SnR3]2 (R ¼ C6F5 (7), C6F3Cl2) (8), (C6Cl5)3
(9)) could be synthesized through a Tamborski type procedure [24],
by treatment of the corresponding triorganotin chloride (4e6) with
potassium under toluene reflux for a prolonged period of time (Eq.
(2)) and isolated as white solids soluble in toluene and partially
soluble in chlorinated solvents and hexane. For this preparation
a sequence involving a reduction of triorganotin halide into
triorganotin hydride followed by a Pd(PPh3)4 promoted decompo-
sition into hydrogen and hexaorgano distannane can be an alter-
native procedure [25].
None of the mass spectra registered for these compounds shows
the molecular ion probably due to the difficulty in ionizing them. A
study on the fragmentation and rearrangement processes in the
mass spectra of tetrakis(pentafluorophenyl) derivatives of group 4
elements evidenced bond formation with involvement of fluorine
abstraction [21]. In the fragmentation of [Sn(C6F5)4] (1) the meta-
stable ions [Sn(C6F5)2F]þ and [Sn(C6F5)F2]þ were observed, which is
explained by elimination of uncharged C6F4 species [21]. In our case
the ESI(ꢀ) spectrum of 1 shows the peak corresponding to the
ꢃ
radical anion [Sn(C6F5)3]ꢀ as the base peak at m/z ¼ 621, besides
ꢃ
other fragments, such as [M ꢀ 4F]ꢀ (m/z ¼ 712, 92%), [Sn(C6F5)2F3]ꢀ
(m/z ¼ 511, 23%) and [Sn(C6F5)2F4]ꢀ (m/z ¼ 530, 17%). Similarly, the
ꢃ
MALDI(ꢀ) spectra of 2 and 3 show the ions [Sn(C6F3Cl2)3]ꢀ (m/
z ¼ 719) and [Sn(C6Cl5)2Cl]ꢀ (m/z ¼ 653), respectively, as the base
peak, and the spectrum of 3 also presents a peak assigned to [Sn
ꢃ
(C6Cl5)3]ꢀ (m/z ¼ 866, 38%).
Toluene reflux
2½SnR3Clꢂ þ 2K
½SnR3ꢂ2þ2KCl
R ¼ C6F5ð7Þ; C6F3Cl2ð8Þ; C6Cl5ð9Þ
(2)
R ¼ C6F5ð4Þ; C6F3Cl2ð5Þ; C6Cl5ð6Þ
72 h
Attempts to prepare triorganotin chlorides by reaction of the
same starting products in the appropriate molar ratio only led to
the expected complex in the case of the pentachlorophenyl deriv-
ative [Sn(C6Cl5)3Cl] (6), while in the other cases the tetraorganotin
compounds 1 and 2 were the only products isolated from the
reaction medium (see Scheme 1). Thus, the triorganotin chlorides
[SnR3Cl] (R ¼ C6F5 (4), C6F3Cl2 (5), C6Cl5 (6)) were synthesized by
a Kocheskov redistribution reaction [22] between the homoleptic
tin complexes SnCl4 and [SnR4] in a 1:3 molar ratio, process that
takes place with a redistribution of ligands (Scheme 1). Complexes
4e6 are isolated as white (4 and 5) or pale yellow (6) air and
moisture-stable solids, soluble in toluene and partially soluble in
chlorinated solvents and hexane.
The 19F NMR spectra of complexes 7 and 8 display the same
pattern than those of the starting products, showing three reso-
nances at ꢀ125.6 (Fo), ꢀ150.3 (Fp) and ꢀ161.8 ppm (Fm) for the
pentafluorophenyl complex or two singlets at ꢀ94.6 and
ꢀ104.5 ppm for the trichlorodifluorophenyl one, in both cases
significantly shifted if compared to those of the starting products.
Although from their 19F NMR spectra it cannot be unambiguously
concluded whether the tinetin bond remains present in solution,
the existence of an equilibrium between [SnR3]2 and 2SnRꢃ3,
described for other hexaorganodistannanes [26], can be excluded
due to presence of only one set of signals in each case in the absence
of other reagents susceptible for transmetallation reactions in
solution.
The 19F NMR spectrum of the pentafluorophenyl derivative 4
is very similar to that registered for 1, displaying three reso-
nances at ꢀ121.9, ꢀ145.0, and ꢀ157.2 ppm (2:1:2) for the ortho,
Regarding the mass spectra, the MALDI(ꢀ) spectrum of 7 shows
the ion [Sn(C6F5)3]ꢀꢃ at m/z ¼ 621 as the base peak. In the MALDI(þ)
spectra of the pentachlorophenyl compound 9 the only fragment
detected was [Sn(C6Cl5)3]þ, located at m/z ¼ 866.
As commented above, we were interested in the study of the
reactivity of the tin compounds synthesized with phosphinegold(I)
complexes in order to prepare new species with Au/Sn metal-
lophilic interactions or to use the tin compounds as arylating
agents. Unfortunately, no reaction was observed between the
mononuclear complexes [SnR4] (1e3) or [SnR3Cl] (4e6) and [AuCl
(PPh3)] or [(AuCl)2(m-dppm)], neither to afford complexes with
intermetallic contacts nor to observe transmetallation reactions,
and the unaltered starting materials were recovered from the
reaction medium in all cases.
When the reaction of [AuCl(PPh3)] with the distannanes 7e9 is
tested, partial decomposition to metallic gold is observed regardless
Scheme 1. Synthesis of complexes 1e6.

R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
2387
of the molar ratio employed. In addition, when the Au/Sn molar ratio
is 2:1, the transmetallation products [AuR(Ph3P)] (R ¼ C6F5 (10),
C6F3Cl2 (11), C6Cl5 (12)) can be isolated from the mother liquors after
extraction with toluene (11, 12) and hexane (10), confirming the
abilityof thedistannanes [SnR3]2 to act asarylatingagents atgold (see
Eq. (3)). Thus, complexes 10e12 were obtained as white (10, 11) or
pale yellow (12) solids, soluble in most common organic solvents and
non-soluble in hexane. Complex 10 had already been prepared by
a different synthetic method [27].
The 31P{1H} NMR spectra of complexes 14 and 15 display
a singlet at 32.4 and 31.1 ppm, respectively, while their 1H NMR
spectra show a triplet located at 3.65 and 3.58 ppm, respectively,
confirming the presence of the diphosphine. The coordination of
the C6F3Cl2 group to gold in 14 is confirmed in its 19F NMR spec-
trum by the appearance of two singlets at ꢀ90.7 and ꢀ116.5 ppm,
signals which appear displaced if compared to those of the start-
ing complex 8, and show similar chemical shifts than in 11. The
base peak in the MALDI(þ) mass spectra of 14 and 15, located at
½AuRðPPh3Þꢂ þ SnR2Cl2 þ Au þ PPh3
R ¼ C6F5ð10Þ; C6F3Cl2ð11Þ; C6Cl5ð12Þ
1=2½SnR3ꢂ2þ2½AuClðPPh3Þꢂ
(3)
In the 31P{1H} NMR spectra of 11 and 12 the singlet due to PPh3
appears shifted up-field if compared to the staring material [AuCl
(PPh3)]: from 33.1 to 42.1 (11) or 39.5 ppm (12), while the 19F NMR
spectrum of 11 displays the typical signals of a dichlorotri-
fluorophenyl group bonded to gold(I). Both the ESI(þ) mass spectra
of compounds 11 and 12 show the highly stable cation [Au(PPh3)2]þ
as the base peak at m/z ¼ 721, as well as peaks due to [Au(PPh3)]þ at
m/z ¼ 459. The cation [M þ Au(PPh3)]þ was also identified in both
cases at m/z ¼ 1117 (11) and 1167.5 (12).
m/z ¼ 977 (14) and 1027 (15), corresponds to the cation [M ꢀ R]þ,
and a peak due to the dinuclear fragment [Au2dppm2]þ is also
observed in both cases at m/z ¼ 1161.
The ionic nature of complex 16 was confirmed by its molar
conductivity in acetone, and the presence of dppm in its 31P{1H}
and 1H NMR spectra, which display resonances at 32.4 and 3.64,
respectively, similar chemical shifts than in the neutral dinuclear
complex 13 (32.1 and 3.67 ppm, respectively). In this case, the
resonances of the fluorine atoms in its 19F NMR spectrum appear at
ꢀ122.2, ꢀ146.1 and ꢀ157.5 ppm, indicating that the C6F5 ligands are
bonded to the tin centre, and also differ from those found in 13
(ꢀ116.4, ꢀ159.1 [3JFeF ¼ 19.9 Hz] and ꢀ163.1 ppm). These signals
start to appear with longer reaction periods, suggesting the transfer
of C6F5 moieties from tin to gold. In the MALDI(þ) mass spectrum of
16 gold-containing fragments are observed, and the molecular
cation appears as the base peak at m/z ¼ 1429, and also the frag-
ment [Au2dppm2]þ (m/z ¼ 1161) could be identified. Finally, in its
MALDI(ꢀ) mass spectrum tin-containing fragments can be detected
and, thus, the molecular anion [Sn(C6F5)3Cl2]ꢀ appears at m/z ¼ 691.
Finally, it is of interest to note that this type of reaction is not
observed with the corresponding SnR4 and SnR3Cl. This different
reactivity could be explained by the homoleptic cleavage of the
tinetin bond in the [SnR3]2 compounds (7e9) resulting in the
formation of radicals of the type SnRꢃ3, which have been detected in
other cases even in solution [26]. This type of radicals cannot be
formed so easily in the case of SnR4 and SnR3Cl, what makes them
less reactive in these type of reaction. The formation of these
radicals could be proved by the careful analysis of their MS spectra.
Thus, although both in the cases of the SnR4 or SnR3Cl, and [SnR3]2
the corresponding MS(ꢀ) spectra show the presence of peaks due
The reactions of the distannanes 7e9 with the dinuclear gold(I)
species [(AuCl)2(m-dppm)] were also carried out in order to evaluate
their capability to act as arylating agents and the possibility of
obtaining a complex with a Au/Sn interaction. When the reaction
of the pentafluorophenyl compound 7 with the gold(I) diphosphine
complex is carried out in a 1:1 molar ratio a mixture of products,
from which the transmetallation product [{Au(C6F5)}2(
already known and structurally characterized [28,29], as well as the
ionic complex [Au3Cl2( -dppm)2][Sn(C6F5)3Cl2], could be identified
m-dppm)],
m
at different reaction times. In contrast, if the same reaction takes
place in a 1:2 molar ratio, although metallic gold is always observed,
independently on the aryl group bonded to tin the transmetallation
reaction product [(AuR)2(
m
-dppm)] (R ¼ C6F5 (13), C6F3Cl2 (14), C6Cl5
(15)) can be isolated as a pure product (Scheme 2). Complexes 14
and 15 are obtained as white (14) or pale yellow (15) air and
moisture-stable solids soluble in most common organic solvents
and non-soluble in hexane.
Moreover, the ionic compound [Au3Cl2(
(16) could also be isolated as a pure species from the reaction of [Sn
(C6F5)3]2 with [(AuCl)2( -dppm)] in a 1:4 molar ratio and with
m-dppm)2][Sn(C6F5)3Cl2]
m
a shorter reaction period (shorter than 15 min). This complex was
obtained as a pale yellowstable solid, which is soluble in chlorinated
solvents and acetone, and non-soluble in diethyl ether and hexane. If
the other perhalophenyl groups are present in the starting tin
compound, the related ionic complexes could not be prepared even
with shorter reaction periods, fact that led us to consider the ionic
product as a possible intermediate in the reaction pathway.
ꢃ
to the radical anion SnRꢀ3 , in the formers their abundance is very
low, while in the case of the hexaorganodistannanes 7 and 9 they
appear as the base peak. This seems to indicate that the reactive
species is the radical SnR3ꢃ , which in the cases of SnR4 and SnR3Cl
need stronger conditions to be formed. According with these
results, although no reaction mechanism studies were carried out,
a radical-chain mechanism [30] could be considered for the
transmetallation of the phosphinegold(I) chlorides with the hexa-
organodistannanes (7e9).
2.2. Crystal structures
Single crystals of 2 and 6$0.5C7H8 were obtained by slow
evaporation of a toluene solution of the complex at room temper-
ature. The former crystallizes in the space group I41/a of the
tetragonal system, while the latter makes it in the space group P-1
of the triclinic system and crystallizes with half a molecule of
solvent per molecule of compound. Both structures contain the tin
centre in a tetrahedral coordination geometry (Figs. 1 and 2),
slightly distorted in the case of 6$0.5C7H8, in which the C(1)eSneC
(11) angle has a value of 118.8(2)ꢁ. The SneC bond lengths are in
Scheme 2. Synthesis of complexes 13e16.

2388
R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
[35]. The comparison of all these SneC lengths seems to indicate:
first, a higher electron-withdrawing effect for the C6Cl5 group if
compared to Cl, which implies that the substitution of a penta-
chlorophenyl group for a chlorine decreases the Lewis acidity of the
tin centre with a subsequent elongation of the SneC distances in
spite of the lower steric demand of the chlorine atom; and, second,
that both C6Cl5 and Cl are better electron-withdrawers than other
aryl groups, such as Tol or Ph. Finally, the SneCl bond length in
6$0.5C7H8, of 2.335(17) Å, compares well with those found in the
related tricloroaryltin chlorides [SnPh3Cl] [33], [Sn(p-Tol)3Cl] [34]
or [SnMes3Cl] [35] (2.321, 2.373 or 2.386(2) Å, respectively).
Single crystals of [Sn(C6F5)3]2 (7) suitable for X-ray diffraction
studies were obtained by slow evaporation of a CHCl3 solution of
the compound at room temperature. The molecular structure of 7
(Fig. 3) contains two Sn(C6F5)3 units connected through a tinetin
single bond, resulting in a tetrahedral coordination geometry for
both tin centers. The SneSn bond length of 2.808(7) Å is close to
double the covalent radium of tin (1.40 Å) and significantly shorter
the double of its van der Waals radium (2.17 Å) [36], which indi-
cates a strong bond with covalent character in solid state. This is
also evident if this distance is compared to those found in other
related tin derivatives containing the units C3SneSnC3, in which the
SneSn bond distances range from 2.72 to 3.08 Å (statistical evalu-
ation made on 32 compounds with SneSn single bond, structures
found in the Cambridge Structural Data Base). The C6F5 moieties
bonded to the tin atoms are orientated in a gauche conformation,
with a torsion angle of 61.4(2)ꢁ, and the SneC bond lengths in 7
(from 2.142(5) to 2.147(5) Å) are of the same order than in [Sn
(C6F5)4] (2.126(8) Å) [4].
Fig. 1. Molecular structure of 2 with the labelling scheme of the atom positions.
Selected bond lengths and angles: SneC 2.133(3) Å, C(1)eSneC(1)#1 107.48(16), C(1)e
SneC(1)#2 110.48(8), C(1)eSneC(1)#3 110.48(8)ꢁ. #1: ꢀx, ꢀy þ 1/2, z; #2: y ꢀ 1/4,
ꢀx þ 1/4, ꢀz þ 1/4; #3: ꢀy þ 1/4, x þ 1/4, ꢀz þ 1/4.
Single crystals of compounds 14$CH2Cl2 and 15 were obtained
by slow diffusion of hexane into a solution of the complex in
dichloromethane. Both molecular structures display the same
general longer in 6$0.5C7H8 (average: 2.163(6) Å) than in 2 (2.133
(3) Å), the latter being similar to those found in [Sn(C6F5)4] [4],
[SnPh4] [31] or [Sn(p-Tol)4] [32] (2.126(8), 2.140(1) or 2.147 Å,
respectively), while the former are longer than the SneC bond
distances in [SnPh3Cl] (2.123 Å) [33] or [Sn(p-Tol)3Cl] (av. 2.118 Å)
[34], and similar to those described for [SnMes3Cl] (av. 2.158(5) Å)
disposition than the related derivatives [{Au(C6F5)}2(
m-dppm)] (13)
[27,28], [{Au(C6F5)}2( m-
m
-PiPr2CH2PPh2)] [29] and [(AuPh)2(
dppm)] [37], all of them showing each gold(I) centre linearly
coordinated to an aryl group and to one of the phosphorus atom of
the bridging bidentate ligand, as well as intramolecular goldegold
contacts (Figs. 4 and 5). The AueP bond lengths, 2.270(3) and 2.300
(3) Å for 14$CH2Cl2 and 2.2882(16) and 2.2715(17) Å for 15, are
Fig. 2. Molecular structure of 6$0.5C7H8 with the labelling scheme of the atom posi-
tions. Selected bond lengths and angles: SneC(1) 2.149(6), SneC(11) 2.169(6), SneC
(21) 2.170(6), SneCl(16) 2.3353(17) Å, C(1)eSneC(11) 118.8(2), C(1)eSneC(21) 105.6
(2), C(11)eSneC(21) 115.8(2), C(1)eSneCl(16) 104.75(18), C(11)eSneCl(16) 98.40(18),
C(21)eSneCl(16) 112.89(17)ꢁ.
Fig. 3. Molecular structure of 7 with the labelling scheme of the atom positions.

R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
2389
similar to the average AueP bond distances found in the com-
pounds mentioned above (2.283, 2.273(2) and 2.300 Å in (13)
[27,28], [{Au(C6F5)}2( m-
-PiPr2CH2PPh2)] [29] and [(AuPh)2(
m
dppm)] [37], respectively). Regarding the AueC bond lengths, of
2.059(12) and 2.067(12) Å for 14$CH2Cl2 and 2.057(6) and 2.070(6)
Å for 15, these are also of the same order than those observed in the
related species cited above, which range from 2.044(5) to 2.063(6)
Å [27,28,37]. The intramolecular goldegold contacts in 14$CH2Cl2
and 15, 3.142(6) and 3.160(4) Å, respectively], compare well with
those described in the crystal structures of [{Au(C6F5)}2(
(13) (3.163(11) Å) [27,28] or [(AuPh)2( -dppm)] (3.154(1) Å) [37],
but are longer than the AueAu distance in [{Au(C6F5)}2(
PiPr2CH2PPh2)] [29] (3.093(3) Å), which contains
different
m-dppm)]
m
m
-
a
bridging ligand [33]. The peculiarity of 14$CH2Cl2 is the evidence of
an additional longer goldegold contact of 3.2126(8) Å between the
gold atoms of two neighbouring molecules, supported by two
additional hydrogen bonds [H(23)eF5#1 ¼2.415(7), C(23)e
F5#1 ¼3.342(7) Å, C(23)eH(23)eF5#1 ¼173.7(7)] none of them
present in the crystal structure of 15.
Finally, single crystals of complex 16$2CH2Cl2 suitable for X-ray
diffraction studies were obtained by slow diffusion of hexane into
a dichloromethane solution of the compound. It crystallizes in Ibca
space group of the orthorhombic system with two molecules of
CH2Cl2 for molecule of complex and only half a molecule and one
CH2Cl2 in the asymmetric unit. The crystal structure of 16$2CH2Cl2
confirms its ionic nature showing isolated cations [Au3Cl2(m-
dppm)2]þ (Fig. 6) and anions [Sn(C6F5)3Cl2]ꢀ (Fig. 7). The structure
of the cation had already been established and reported in previous
works with different anions: [Au(C6F5)3Cl]ꢀ [38], Clꢀ [39], ClOꢀ4
[40], PFꢀ6 [41], and it exhibits a triangular Au3 core with intermo-
lecular aurophilic interactions between the three metals of 3.1282
(7) (two of them) and 3.2268(12) Å. The same trend in the AueAu
distances is observed in other salts, which display distances of
3.1525(4), 3.1922(4) and 3.2770(4) Å in the hexafluorophosphate
[41], 3.0663(5), 3.1645(5) and 3.6784(4) Å in the [Au(C6F5)3Cl]ꢀ
derivative [38], 3.076(1) (two distances) and 3.729(1) Å in the
chloride [39] and 3.0883(8), 3.1738(6) and 3.4500(8) Å in the
Fig. 5. Molecular structure of 15 with the labelling scheme of the atom positions.
Hydrogen atoms have been omitted for clarity.
Fig. 4. Molecular structure of 14$CH2Cl2 with the labelling scheme of the atom posi-
Fig. 6. Crystal structure of the cation of 16$2CH2Cl2 with the labelling scheme of the
tions. Hydrogen atoms have been omitted for clarity.
atom positions. Hydrogen atoms have been omitted for clarity.

2390
R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
result is obtained when the Au/Sn ratio is modified in its reaction
with [(AuCl)2( -dppm)], leading to a ionic complex with a gold
m
cation and a tin anion.
This different behaviour could be explained by the easier
homoleptic cleavage of the tinetin bond in [SnR3]2, resulting in the
formation of radicals of the type SnRꢃ3 observed in their MS spectra,
than in the case of SnR4 and SnR3Cl, making the latter less reactive
and suggesting a radical-chain mechanism for the transmetallation
reactions.
4. Experimental
4.1. Instrumentation
All manipulations with the organotin compounds were carried
out under an argon atmosphere using standard Schlenk techniques.
All solvents were collected from an MBraun MB SPS-800 distillation
column before use. The 19F, 1H and 31P{1H} NMR spectra were
recorded on a Bruker ARX 300 spectrometer in CDCl3. The MS-ESI
spectra were recorded with a microOTOF-Q-Bruker, using the ESI
technique. The MALDI mass spectra were registered on a Microflex
Bruker spectrometer using DIT (Dithranol) as matrix. The m/z
values are given for the higher peak in the isotopic pattern, and the
used equipment did not allow an unambiguous discrimination
between ions and radical ions. The C, H analyses were carried out
with a Perkin-Elmer 240C microanalyzer.
Fig. 7. Crystal structure of the anion of 16$2CH2Cl2 with the labelling scheme of the
atom positions.
perchlorate [40]. As can be deduced from these distances, only in
16$2CH2Cl2 and in the hexafluorophosphate salt the three gold
atoms maintain aurophilic contacts, while in the rest only two
Au/Au interactions are observed. The AueCl and AueP bond
lengths in the cation of 16$2CH2Cl2 are 2.315(3) Å, and 2.218(3) and
2.318(3) Å, respectively, the latter indicating a higher trans influ-
ence for the phosphorus donor ligand than for the chloride, as had
also been observed in the other salts [38e41].
4.2. General
Sn(C6F5)4 (1) [4], [AuCl(PPh3)] [43] and [(AuCl)2(m-dppm)] [44]
were synthesized according to literature procedures. No reaction
was observed between the mononuclear complexes [SnR4] (1e3) or
[SnR3Cl] (4e6) and [AuCl(PPh3)] or [(AuCl)2(m-dppm)], under the
general reaction conditions: CH2Cl2 as solvent, room temperature
and 1 h mixing.
The structure of theanion in 16$2CH2Cl2 containsthe tincentrein
a trigonal bipyramidal environment with the chlorine atoms occu-
pying theapical positions andthe aryl groups in theequatorial plane.
The SneCipso bond lengths (2.140(16) and 2.157(11) Å) compare well
with those found in [Sn(C6F5)4] (2.126(8) Å) [4], in 2 (2.133(3) Å) and
in the hexaoragonodistannane 7 (2.142(5)e2.147(5) Å). In contrast,
the SneCl bond length in 16$2CH2Cl2 (2.498(3) Å) is longer than in
the pentachlorophenyl derivative 6$0.5C7H8 (2.3353(17) Å).
The importance of hydrogen bonding in crystal packing has
4.3. Synthesis of [SnR4] (R ¼ C6F3Cl2 (2), C6Cl5 (3))
Complexes 2 and 3 were prepared followinga similarprocedure to
that reported for 1 [4]. A freshly prepared solution of LiR [13 mmol;
2.68 g(2), 3.33 g(3)]indiethyl etheratꢀ60 ꢁC wasaddeddropwise to
a cooled (ꢀ60 ꢁC) diethyl ether suspension of SnCl4 (3.26 mmol,
0.85 g). The reaction mixture was stirred at that temperature for 1 h
and then allowed to slowly warm to room temperature and stirred for
8 h. The resulted white suspension was evaporated to dryness in
vacuum and 30 mL of toluene added. After removal of the LiCl by
filtration, the solution was concentrated to 5 mL and the products
crystallized as white (2) or pale yellow (3) solids.
been discussed [42] and in the case of [Au3Cl2(m-dppm)2][PF6],
where hydrogen bonding involving the anions in is extensive, it has
been concluded that the hydrogen-bonded interactions in the
lattice have a certain influence on the geometry of the Au3 cluster in
salts containing the cation [Au3Cl2(m
-dppm)2]þ [41]. A closer look
into the crystal packing of 16$2CH2Cl2 also evidenced an extensive
hydrogen bonding network, in which the cation, the anion and the
solvent molecule are involved.
4.3.1. Compound (2)
Yield: 80%. Elemental analysis (%) calcd for C24Cl8F12Sn: C 31.38;
found: C 31.44.19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ95.7 (s, 8F, Fo) and
ꢀ104.4 (s, 4F, Fp). MS-MALDI(ꢀ) m/z (%): 719 [Sn(C6F3Cl2)3]ꢀꢃ (100).
3. Conclusions
4.3.2. Compound (3)
The perhalophenyltin derivatives (1e6) showed no reactivity
toward the phosphine gold(I) chlorides, indicating that, although
the perhalophenyl groups increase the Lewis acidity of the tin
centre, they do not increase their Lewis acidity as much as neces-
sary to react with gold(I) precursors.
The hexaorganodistannanes (7e9) behave in a different manner
than expected, and their reactivity toward phosphine gold(I)
chlorides showed their ability to transfer the perhalophenyl moiety,
making them potential candidates as arylating agents for gold(I).
Only in the case of the pentafluorophenyl derivative 7 a different
Yield: 86%. Elemental analysis (%) calcd for C24Cl20Sn: C 25.83;
found: 26.01. MS-MALDI(ꢀ) m/z (%): 653 [Sn(C6Cl5)2Cl]ꢀ (100), 866
ꢃ
[Sn(C6Cl5)3]ꢀ (38).
4.4. Synthesis of [SnR3Cl] (R ¼ C6F5 (4), C6F3Cl2 (5), C6Cl5 (6))
Method A: 0.2 mmol of SnCl4 (0.023 mL) and 0.6 mmol of [SnR4]
(R ¼ C6F5, 0.47 g; R ¼ C6F3Cl2, 0.56 g; R ¼ C6Cl5, 0.67 g) were mixed
in a schlenck under argon atmosphere and the mixture was stirred
at reflux temperature for 48 h. Toluene was then added to the

R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
2391
Table 2
reaction mixture and evaporation of the solvent led to the product
as a white (4 and 5) or pale yellow (6) crystalline solid.
Details of data collection and structure refinement for complexes 14$CH2Cl2, 15 and
16$2CH2Cl2.
Method B: Complex 6 can alternative be prepared as follows:
a freshly prepared diethyl ether solution of Li(C6Cl5) (13 mmol,
3.35 g) at ꢀ78 ꢁC was added dropwise to a cooled suspension of
SnCl4 (4.3 mmol, 1.13 g) in the same solvent. The reaction mixture
was stirred at that temperature for 2 h and then allowed to slowly
warm to room temperature while stirring for 12 more hours. The
resulting yellow solution was evaporated to dryness in vacuum, and
the remaining solid extracted with toluene (30 mL). After removal of
the LiCl formed by filtration, the toluene solution was concentrated
to 5 mL, which leads to the crystallization of 6 as a pale yellow solid.
Compound
Formula
Formula weight
Crystal system
Space group
a (Å)
14$CH2Cl2
15
16$2CH2Cl2
C38H22Au2Cl6F6P2 C37H22Au2Cl10P2 C70H48Au3Cl8F15P4Sn
1261.1
Monoclinic
C2/c
12.1549(4)
23.3186(7)
28.3386(9)
90
101.6060(10)
90
7867.9(4)
8
1276.92
Triclinic
P-1
2291.15
Orthorhombic
Ibac
21.3816(8)
23.8841(9)
32.4186(10)
90
10.0208(7)
13.6820(14)
16.0957(15)
98.419(5)
101.343(5)
110.234(5)
1974.2(3)
2
120(2)
2.148
19343
0.0640
b (Å)
c (Å)
a
(ꢁ)
b
(&deg)
90
90
g
(ꢁ)
V (Å3)
Z
16555.5(10)
8
120(2)
6.006
60210
0.0971
9903
4.4.1. Compound (4)
T (K)
120(2)
7.997
Yield: 84%. Elemental analysis (%) cacld for C18ClF15Sn: C 32.99;
m(Mo K
a
)(mmꢀ1
)
found C 32.56. 19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ121.9 (m, 6F, Fo),
Reflections collected 29501
R(int)
3
ꢀ145.0 (t, 3F, Fp, JFpeFm ¼ 19.9 Hz), ꢀ157.2 (m, 6F, Fm). MS-MALDI
0.0880
9343
1.087
ꢃ
(ꢀ) m/z (%): 621 [M ꢀ Cl]ꢀ (100).
Unique reflections
8889
1.023
GOF on F2
1.044
Final R indices[I > 2
(I)]: R1, wR2
s
0.0693, 0.1887
0.0430, 0.0993 0.0704, 0.2271
4.4.2. Compound (5)
Yield: 51%. Elemental analysis (%) cacld for C18Cl7F9Sn: C 28.67;
found C 28.59. 19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ95.9 (s, 6F, Fo),
ꢃ
ꢀ101.7 (s, 3F, Fp); MS-ESI(ꢀ) m/z (%): 719 [M ꢀ Cl]ꢀ (100).
4.5.2. Compound (8)
Yield: 43%. Elemental analysis (%) cacld for C36Cl12F18Sn2: C
30.09; found: C 29.96. 19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ94.6 (s,
4.4.3. Compound (6)
Yield: 64%. Elemental analysis (%) cacld for C18Cl16Sn:C 23.96; found
12F, Fo), ꢀ104.5 (s, 6F, Fp).
C 23.87. MS-ESI(ꢀ) m/z (%): 653 [M ꢀ C6Cl5]ꢀ (15), 866 [M ꢀ Cl]ꢀꢃ (50).
ꢃ
4.5.3. Compound (9)
Yield: 65%. Elemental analysis (%) cacld for C36Cl30Sn2: C 24.95;
4.5. Synthesis of [SnR3]2 (R ¼ C6F5 (7), C6F3Cl2 (8), C6Cl5 (9))
ꢃ
found: C 24.35. MS-MALDI(ꢀ) m/z (%): 866 [Sn(C6Cl5)3]ꢀ (100).
To a toluene solution of 1 mmol of [SnR3Cl] (0.66 g (4), 0.76 g (5)
or 0.91 g (6)) an excess of potassium (1.28 mmol, 0.05 g) was added
and the reaction mixture was stirred under reflux for 72 h. The
followed KCl formed and the excess of potassium were then filtered
off and the resulting pale yellow solution was concentrated by
evaporation in vacuum, and the hexaorganodistannanes were iso-
lated as white crystalline solids.
4.6. Synthesis of [AuR(PPh3)] (R ¼ C6F5 (10) C6F3Cl2 (11), C6Cl5 (12))
To a dichloromethane solution of [AuCl(PPh3)] (0.5 mmol,
0.25 g) 0.125 mmol of the corresponding [SnR3]2 (0.157 g (7),
0.181 g (8) or 0.219 g (9)) was added at room temperature. After
30 min of stirring the solvent was evaporated in vacuum, 20 mL of
toluene were then added, and the metallic gold formed was filtered
off. The remaining solution was concentrated and hexane (20 mL)
was added to precipitate the new complex as a white (10 and 11) or
pale yellow (12) solid.
4.5.1. Compound (7)
Yield: 46%. Elemental analysis (%) cacld for C36F30Sn2: C 34.88;
found: C 33.99. 19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ125.6 (m, 12F,
3
Fo), ꢀ150.3 (t, 6F, Fp, JFpeFm ¼ 19.8 Hz), ꢀ161.8 (m, 12F, Fm). MS-
ꢃ
MALDI(ꢀ) m/z (%): 621 [Sn(C6F5)3]ꢀ (100).
4.6.1. Compound (10)
Yield: 63%.
Table 1
Details of data collection and structure refinement for complexes 2, 6$0.5C7H8 and 7.
4.6.2. Compound (11)
Yield: 51%. Elemental analysis (%) cacld for C24H15AuCl2F3P: C
Compound
Formula
Formula weight
Crystal system
Space group
a (Å)
2
6$0.5C7H8
C21.5Cl20Sn
948.14
Triclinic
P-1
7
43.71, H 2.29; found: C 43.62, H 2.19. 31P{1H} NMR (300 MHz, CDCl3,
C24Cl8F12Sn
918.53
Tetragonal
I41/a
18.2659(16) 8.6675(5)
18.2659(16) 11.2763(6)
8.5992(7)
90
90
C36F30Sn2
1239.74
Triclinic
P-1
9.6823(3)
10.6163(4)
10.8894(4)
99.896(2)
113.346(2)
108.891(2)
ppm):
d
42.1 (s). 19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ90.2 (s, 2F, Fo),
7.40e7.66 (m,
ꢀ116.3 (s, 1F, Fp). 1H NMR (300 MHz, CDCl3, ppm):
d
b (Å)
Table 3
c (Å)
18.1720(9)
92.763(3)
103.050(3)
94.451(3)
1721.04(16) 2256(5)
2
Selected bond lengths [Å] and angles [ꢁ] for complex 7.
a
(ꢁ)
SneC(1)
2.147(5)
2.142(5)
2.144(5)
2.8081(7)
b
(&deg)
SneC(11)
SneC(21)
SneSn#1
g
(ꢁ)
90
2869.1(4)
4
V (Å3)
Z
1
T (K)
120(2)
1.733
7349
0.0756
1739
1.017
120(2)
2.000
12338
0.0426
6574
1.059
0.0509,
0.1435
120(2)
1.554
13237
0.0479
4302
1.123
0.0489,
0.1173
C(11)eSneC(21)
C(11)eSneC(1)
C(21)eSneC(1)
C(11)eSneSn#1
C(21)eSneSn#1
C(1)eSneSn#1
109.24(16)
107.70(17)
110.26(17)
111.88(12)
109.38(12)
108.36(12)
m
(Mo K
a
)(mmꢀ1
)
Reflections collected
R(int)
Unique reflections
GOF on F2
Final R indices[I > 2
s
(I)]: R1, wR2 0.0398,
0.0662
Symmetry transformations used to generate equivalent
atoms: #1 ꢀx þ 1, ꢀy þ 1, ꢀz þ 1.

2392
R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
Table 4
Selected bond lengths [Å] and angles [ꢁ] for complex 14$CH2Cl2.
Table 6
Selected bond lengths [Å] and angles [ꢁ] for complex 16$2CH2Cl2.
Au(1)eC(1)
Au(2)eC(11)
Au(1)eP(1)
Au(2)eP(2)
Au(1)eAu(2)
Au(1)eAu(1)#1
2.059(12)
2.067(12)
2.300(3)
2.270(3)
3.1422(6)
3.2126(8)
Au(1)eAu(2)
Au(2)eAu(2)#1
Au(1)eP(1)
Au(2)eP(2)
Au(2)eCl(2)
SneC(1)
3.1282(7)
3.2268(12)
2.318(3)
2.218(3)
2.315(3)
2.140(16)
2.157(11)
2.498(3)
SneC(11)
SneCl(1)
C(1)eAu(1)eP(1)
C(1)-Au(1)-Au(2)
171.3(3)
92.3(3)
P(1)eAu(1)eAu(2)
C(1)eAu(1)eAu(1)#1
P(1)eAu(1)eAu(1)#1
Au(2)eAu(1)eAu(1)#1
C(11)eAu(2)eP(2)
C(11)eAu(2)eAu(1)
P(2)eAu(2)eAu(1)
88.68(7)
82.9(2)
100.68(7)
149.01(2)
175.3(3)
94.9(3)
P(1)#1eAu(1)eP(1)
P(2)eAu(2)eCl(2)
Au(2)#1eAu(1)eAu(2)
Au(1)eAu(2)eAu(2)#1
Cl(1)#2eSneCl(1)
C(1)eSneC(11)
C(11)eSneC(11)#2
C(11)eSneCl(1)#2
C(1)eSneCl(1)
172.79(16)
171.83(12)
62.10(2)
58.952(12)
175.20(15)
118.1(3)
123.8(6)
89.2(3)
89.79(7)
Symmetry transformations used to generate equivalent atoms: #1
ꢀx þ 1, y, ꢀz þ 1/2.
92.40(7)
88.6(3)
C(11)eSneCl(1)
Symmetry transformations used to generate equivalent atoms: #1
x, ꢀy, ꢀz þ 1/2 #2 ꢀx þ 3/2, y þ 0, ꢀz þ 1.
15H, C6H5). MS-ESI(þ) m/z (%): 459 [Au(PPh3)]þ (25), 721 [Au
(PPh3)2]þ (100), 1117 [MþAu(PPh3)]þ (6).
4.6.3. Compound (12)
4.7.3. Compound (15)
Yield: 60%. Elemental analysis (%) cacld for C24H15AuCl5P: C
Yield: 67%. Elemental analysis (%) cacld for C37H22Au2Cl10P2: C
40.66, H 2.13; found: C 40.56, H 2.05. 31P{1H} NMR (300 MHz,
34.78, H 1.74; found: C 34.69, H 1.66. 31P{1H} NMR (300 MHz, CDCl3,
d
39.5 (s). 1H NMR (300 MHz, CDCl3, ppm):
ppm): d d 3.58 (t, 2H, CH2,
31.1 (s). 1H NMR (300 MHz, CDCl3, ppm):
CDCl3, ppm):
7.38e7.71 (m, 15H, C6H5). MS-ESI(þ) m/z (%): 459 [Au(PPh3)]þ
2JPH ¼ 11 Hz), 7.39e7.72 (m, 20H, C6H5). MS-MALDI(þ) m/z (%):
d
(23), 721 [Au(PPh3)2]þ (100), 1167 [M þ Au(PPh3)]þ (2).
1027 [M ꢀ C6Cl5]þ (100), 1161 [Au2dppm2]þ (38).
4.7. Synthesis of [(AuR)2(
C6Cl5 (15))
m
-dppm)] (R ¼ C6F5 (13), C6F3Cl2 (14),
4.8. Synthesis of [Au3Cl2(
m-dppm)2][Sn(C6F5)3Cl2] (16)
To a solution of [(AuCl)2(
m
-dppm)] (0.2 mmol, 0.16 g) in CH2Cl2
To a dichloromethane solution of [(AuCl)2(m-dppm)] (0.2 mmol,
at room temperature 4 (0.05 mmol, 0.061 g) was added. The
reaction mixture was stirred for 15 min, the metallic gold formed
was filtered off, and the resulting pale yellow solution was evap-
orated, obtaining complex 16 as a pale yellow solid. Yield: 49%.
Elemental analysis (%) cacld for C70H48Au3Cl8F15P4Sn: C 36.67, H
2.11; found: C 36.60, H 2.04. 31P{1H} NMR (300 MHz, CDCl3, ppm):
0.16 g) the corresponding hexaorgano distannane (0.1 mmol,
0.124 g (7); 0.141 g (8); 0.17 g (9)) was added at room temperature.
After stirring for 30 min and filtering off the metallic gold formed,
the solution was evaporated to ca 5 mL, and the product was
precipitated with hexane as a white (13 and 14) or pale yellow (15)
solid.
d
32.4 (s). 19F NMR (300 MHz, CDCl3, ppm):
d
ꢀ122.2 (m, 6F, Fo),
3
ꢀ146.1 (m, 3F, Fp, JFpeFm ¼ 19.8 Hz), ꢀ157.5 (m, 6F, Fm); 1H NMR
4.7.1. Compound (13)
(300 MHz, CDCl3, ppm):
d
3.64 (m, 4H, CH2), 7.39ꢀ7.67 (m, 40H,
Yield: 62%.
C6H5). MS-MALDI(þ) m/z (%): 1161 [Au2dppm2]þ (70), 1429
[Au3Cl2(
m
-dppm)2]þ (100). MS-MALDI(ꢀ) m/z (%): 691 [Sn
4.7.2. Compound (14)
(C6F5)3Cl2]ꢀ (85). LM (acetone) ¼ 102
U .
ꢀ1 cm2 molꢀ1
Yield: 75%. Elemental analysis (%) cacld for C37H20Au2Cl4F6P2: C
37.76, H 1.71, found C: 37.70, H 1.69. 31P{1H} NMR (300 MHz, CDCl3,
ppm): d d 3.65 (t, 2H, CH2,
32.4 (s). 1H NMR (300 MHz, CDCl3, ppm):
4.9. Crystallography
2JPH ¼ 11 Hz), 7.39e7.67 (m, 20H, C6H5). 19F NMR (300 MHz, CDCl3,
ppm):
d
ꢀ90.7 (s, 4F, Fo), ꢀ116.5 (s, 2F, Fp). MS-MALDI(þ) m/z (%):
The crystals were mounted in inert oil on a glass fibre and
transferred to the cold gas stream of a Nonius Kappa CCD diffrac-
tometer equipped with an Oxford Instruments low temperature
977 [M ꢀ C6F3Cl2]þ (100), 1161 [Au2dppm2]þ (9).
attachment. Data were collected using monochromated Mo K
a
Table 5
radiation ( and . Absorption correc-
l
¼ 0.71073 Å). Scan type
u
4
Selected bond lengths [Å] and angles [ꢁ] for complex 15.
tions: semiempirical (based on multiple scans). The structures were
refined on F2 using the program SHELXL-97 [45]. All non-hydrogen
atoms were refined anisotropically. Hydrogen atoms were included
using a riding model. Further details of the data collection and
refinement are given in Tables 1 and 2 and main bind distances and
angles in Tables 3e6.
Au(1)eC(1)
Au(1)eP(1)
Au(1)eAu(2)
Au(2)eC(11)
Au(2)eP(2)
2.070(6)
2.2882(16)
3.1602(4)
2.057(6)
2.2715(17)
C(1)eAu(1)eP(1)
C(1)eAu(1)eAu(2)
P(1)eAu(1)eAu(2)
175.55(17)
101.78(16)
79.27(5)
Acknowledgement
C(11)eAu(2)eP(2)
C(11)eAu(2)eAu(1)
P(2)eAu(2)eAu(1)
174.67(17)
89.35(16)
94.18(5)
This work was supported by the D.G.I.(MEC)/FEDER (CTQ2010-
20500-C02-02).

R.V. Bojan et al. / Journal of Organometallic Chemistry 695 (2010) 2385e2393
2393
D. Joosten, I. Weissinger, M. Kirchmann, C. Maichle-Mossmer,
F.M. Schappacher, R. Pottgen, L. Wesemann, Organometallics 26 (2007) 5696.
[20] B. Findeis, M. Contel, L.H. Gade, M. Laguna, M.C. Gimeno, I.J. Scowen,
M. McPartlin, Inorg. Chem. 36 (1997) 2386.
Appendix A. Supplementary material
CCDC 779061-779066 contain the supplementary crystallo-
graphic 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.
[21] J.M. Miller, Can. J. Chem. 47 (1969) 1613.
[22] K.A. Kocheshkov, Ber. Deutsch. Chem. Gesell. 62 (1926) 996.
[23] M.N. Bochkarev, G.A. Razuvaev, N.S. Vyazankin, Russ. Chem. Bull. 24 (1975) 1701.
[24] G.J. Chen, C. Tamborski, J. Organomet. Chem. 251 (1983) 149;
C. Tamborski, E.J. Soloski, J. Am. Chem. Soc. 83 (1961) 3734.
[25] N.A. Bumagin, Yu.V. Gulevich, I.P. Beletskaya, Izvest Akad, Nauk SSSR, Ser.
Khim. (1984) 1137;
References
T.N. Mitchell, A. Amamria, H. Killing, D. Rutschow, J. Organomet. Chem. 304
(1986) 257.
[26] A.F. El-Farargy, M. Lehnig, W.P. Neumann, Chem. Ber. 115 (1980) 2783.
[27] R.W. Baker, P.J. Pauling, J. Chem. Soc. Dalton Trans. (1972) 2264.
[28] P.G. Jones, C. Thone, Acta Crystallogr. Sect. C: Cryst. Struct. Commun. 48 (1992)
1312.
[29] M. Bardaji, P.G. Jones, A. Laguna, M.D. Villacampa, N. Villaverde, Dalton Trans.
(2003) 4529.
[30] D. Seyferth, F.M. Armbrecht, B. Schneider, J. Am. Chem. Soc. 91 (1969) 1954;
H.C. Clark, J.H. Tsai, Chem. Commun. (1965) 111;
H.C. Clark, J.D. Cotton, J.H. Tsai, Can. J. Chem. 44 (1966) 903;
W.R. Cullen, D.S. Dawson, G.E. Styan, J. Organomet. Chem. 3 (1965) 406;
J.S. Shapiro, F.P. Lossing, J. Phys. Chem. 72 (1968) 1552.
[31] P.C. Chieh, J. Trotter, J. Chem. Soc. A (1970) 911;
N.A. Akmed, G.G. Aleksandrov, J. Struct. Chem. (Russ.) 11 (1970) 824.
[32] A. Karipides, K. Wolfe, Acta Crystallogr. Sect. B 31 (1975) 605.
[33] N.G. Bokii, G.N. Zakharova, Yu.T. Stuchkov, Zh. Strukt, Khim. (Russ.) 11 (1970)
895.
[34] J.M. Geller, I.S. Butler, D.F.R. Gilson, F.G. Morin, I. Wharf, F. Belanger-Gariepy,
Can. J. Chem. 81 (2003) 1187.
[35] J. Geller, I. Wharf, F. Belanger-Gariepy, A.-M. Lebuis, I.S. Butler, D.F.R. Gilson,
Acta Crystallogr. Sect. C 58 (2002) m466.
[1] M.A. Garcias-Monforte, P.J. Alonso, J. Fornies, B. Menjon, Dalton Trans. (2007)
3347.
[2] E. Vedejs, D.E. Erdman, D.R. Powell, J. Org. Chem. 58 (1993) 2840;
J. Chen, K. Sakamoto, A. Orita, J. Otera, Synlett (1996) 877.
[3] J. Chen, K. Sakamoto, A. Orita, J. Otera, J. Organomet. Chem. 574 (1999) 58.
[4] C. Tamborski, E.J. Soloski, S.M. Dec, J. Organomet. Chem. 4 (1965) 446;
A. Karipides, C. Forman, R.H.P. Thomas, A.T. Reed, Inorg. Chem. 13 (1974) 811.
[5] H. Preut, H.-J. Haupt, F. Huber, Z. Anorg, Allg. Chem. 396 (1973) 81;
K. Ekardt, H. Fuess, M. Hattori, R. Ikeda, H. Ohki, A. Weiss, Z. Naturforsch.,
A: Phys. Sci. 50 (1995) 758;
D. Dakternieks, Fong Sheen Kuan, A. Duthie, E.R.T. Tiekink, Main Group Met.
Chem. 24 (2001) 65.
[6] C. Schneider-Koglin, K. Behrends, M. Drager, J. Organomet. Chem. 448 (1993) 29.
[7] C. Schneider, M. Drager, J. Organomet. Chem. 415 (1991) 349.
[8] H. Puff, B. Breuer, G. Gehrke-Brinkmann, P. Kind, H. Reuter, W. Schuh,
W. Wald, G. Weidenbruck, J. Organomet. Chem. 363 (1989) 265.
[9] F.P. Pruchnik, M. Banbula, Z. Ciunik, H. Chojnacki, B. Skop, M. Latocha,
T. Wilczok, J. Inorg. Biochem. 90 (2002) 149.
[10] A.G. Davies, Organotin Chemistry, second ed. WILEY-VCH Verlag, Weinheim, 2004.
[11] A.L.J. Beckwith, P.E. Pigon, Austral. J. Chem. 39 (1986) 77.
[12] G. Tagliavini, L. Doretti, J. Chem. Soc. Chem. Commun. (1966) 562.
[13] J. Otera, T. Kadowaki, R. Okawara, J. Organomet. Chem. 19 (1969) 213.
[14] T.N. Mitchell, A. Amamria, H. Killing, D. Rutschow, J. Organomet. Chem. 304
(1986) 257;
[36] J. Emsley, Die Elemente. Walter de Gruyter, Berlin, 1994.
[37] X. Hong, K.K. Cheung, C.X. Guo, C.M. Che, J. Chem. Soc., Dalton Trans. (1994)
1867.
[38] R. Uson, A. Laguna, M. Laguna, E. Fernandez, M.D. Villacampa, P.G. Jones,
G.M. Sheldrick, J. Chem. Soc. Dalton Trans. (1983) 1679.
[39] I.J.B. Lin, J.M. Hwang, Da-Fa Feng, M.C. Cheng, Yu Wang, Inorg. Chem. 33
(1994) 3467.
[40] T.L. Zhang, Y. Qin, C.G. Meng, Acta Cryst. E61 (2005) m2588.
[41] E.C. Constable, C.E. Housecroft, M. Neuburger, S. Schaffner, E.J. Shardlow, Acta
Cryst. E63 (2007) m1698.
T.N. Mitchell, N.M. Dornseifer, A. Rahm, J. High Pressure Res. 7 (1991) 165.
[15] H.G. Kuivila, K.R. Wursthorn, G.F. Smith, J. Am. Chem. Soc. 100 (1978) 2779;
K.R. Wursthorn, H.G. Kuivila, J. Organomet. Chem. 140 (1977) 29;
N.A. Bumagin, Yu.V. Gulevich, I.P. Beletskaya, J. Organomet. Chem. 282 (1985)
421.
[16] J.W. McIntee, Ch. Sundararajan, A.C. Donovan, M.S. Kovacs, A. Capretta,
J.F. Valliant, J. Org. Chem. 73 (2008) 8236.
[42] F. Mendizabal, P. Pyykkö, N. Runeberg, Chem. Phys. Lett. 370 (2003) 733.
[43] R. Usón, A. Laguna, Organomet. Synth. 3 (1985) 325.
[44] H. Schmidbaur, A. Wohlleben, F. Wagner, O. Orama, G. Huttner, Chem. Ber.
110 (1977) 1748;
R. Usón, A. Laguna, J. Vicente, J. García, Rev. Acad. Ciencias Zaragoza 31 (1976)
77.
[45] G.M. Sheldrik, SHELX-97: A Program for Crystal Structure Refinement. Uni-
versität Göttingen, Göttingen, Germany, 1997.
[17] Z. Demidowicz, R.L. Johnston, J.C. Achell, D.M.P. Mingos, I.D. Williams, J. Chem.
Soc. Dalton Trans. (1988) 1751.
[18] D.M.P. Mingos, H.R. Powell, T.L. Stolbert, Transition Met. Chem. 17 (1992) 334.
[19] T. Marx, B. Mosel, I. Pantenburg, S. Hagen, H. Schulze, L. Wesemann, Chem.
Eur. J. 9 (2003) 4472;
S. Hagen, I. Pantenburg, F. Weigend, C. Wickleder, L. Wesemann, Angew.
Chem., Int. Ed. 42 (2003) 1501;
S. Hagen, L. Wesemann, I. Pantenburg, Chem. Commun. (2005) 1031;