Syntheses, Structures, and Complexation Studies of Tris(organostannyl)methane Derivatives

Article abstract of DOI:10.1002/open.201600092

The syntheses of tris(organostannyl)methanes HC(SnX_nPh_(3-n))₃ (1, n=0; 2, n=1, X=I; 3, n=1, X =F; 4, n=1, X=Cl; 5, n=1, X=OAc; 6, n=2, X=I; 7, n=2, X=Cl) and the organostannate complexes Et₄N[HC(SnIPh₂

Full text of DOI:10.1002/open.201600092

DOI: 10.1002/open.201600092
Syntheses, Structures, and Complexation Studies of
Tris(organostannyl)methane Derivatives
Anicet Siakam Wendji, Michael Lutter, Lukas M. Stratmann, and Klaus Jurkschat*[a]
The syntheses of tris(organostannyl)methanes HC(SnXnPh(3-n) 3
)
IR spectroscopy, electrospray mass spectrometry, and (with the
(1, n=0; 2, n=1, X=I; 3, n=1, X =F; 4, n=1, X=Cl; 5, n=1,
X=OAc; 6, n=2, X=I; 7, n=2, X=Cl) and the organostannate
complexes Et4N[HC(SnIPh2)3·F] (8), Ph4P[HC(SnClPh2)3·Cl] (9), and
[Ph4P]2[HC(SnCl2Ph)3·2Cl] (10) are reported. The compounds
exception of 3) single-crystal X-ray diffraction analysis. From
the reaction between
2
and AgClO4 resulted the
organotin oxocluster
unprecedented hexanuclear
[HC{Sn(ClO4)2Ph2}2Sn(OH)2Ph]2 (11), the molecular structure of
which was elucidated by using X-ray crystallography.
1
were characterized by H, 13C, 19F, and 119Sn NMR spectroscopy,
1. Introduction
The design and synthesis of molecular hosts for the selective
recognition of anions continue to attract considerable atten-
tion in the field of supramolecular host–guest chemistry.[1–19]
The growing interest in such compounds is stimulated by their
potential applications in biological processes including anion
transport, in chemical catalysis, as well as in environmental
and health issues.[20–23] Examples of anion receptors that make
use of the Lewis acidity of organoelement/organometallic moi-
eties or metal cations have been reported to be efficient in co-
ordinating anions and neutral Lewis bases,[24–30] as well as in
anion sensing,[16–18,30–46] small molecule activation,[47–51] and or-
ganometallic catalysis.[52–54] An alternative strategy used to in-
crease the anion affinity of such systems involves two Lewis
acids in
a bicentric motif that support anion chela-
tion.[16,35,37,40,55–74] As part of our contribution to this field of re-
search, we have investigated bicentric[28h,k–l] and multicen-
tric[28m] Lewis acids of type A, B, C, and D (Scheme 1) contain-
ing two and three tin atoms, respectively, and have proven
their ability to complex halide anions in dichloromethane solu-
tion and to selectively recognize the phosphate anion. Recent-
ly, we reported the open-chain and cyclic compounds of
types E–G, containing both silicon and tin atoms and the cor-
responding salts containing the complex anions.[75] Notably,
among these compounds the simple methylene-bridged repre-
Scheme 1. Selected bi- and multicentric tin- and silicon-based Lewis acids
holding potential for anion complexation.
sentative CH2(SnFR2)2 (R=Ph, n-octyl) is among the most effi-
cient host for fluoride anion.[28n–o] In this context, it is surprising
that, although reported as early as 1933,[76,77a] the reactivity/de-
rivatization of tris(triphenylstannyl)methane, HC(SnPh3)3, was
not investigated to date. On the other hand, there is one
report describing the synthesis and reactivity of tris(trimetyl-
stannyl)methane, HC(SnMe3)3,[77b] and one report discussing
the molecular structure of tris(trimethylstannyl) acetonitrile,
(Me3Sn)3CCN.[77c] With this in mind and in continuation of our
previous work mentioned above, we have synthesized and
structurally characterized the organotin compounds of type H
and I (Scheme 1). Herein, we show that the iodine- and chlor-
ine-substituted representatives of H- and I-type compounds
are capable of binding fluoride and chloride anions, respective-
ly. Also reported is the reaction of the iodine-substituted repre-
[a] A. S. Wendji, M. Lutter, L. M. Stratmann, Prof. Dr. K. Jurkschat
Lehrstuhl für Anorganische Chemie II
Fakultät für Chemie und Chemische Biologie
Technische Universität Dortmund
44221 Dortmund (Germany)
E-mail: klaus.jurkschat@tu-dortmund.de
Supporting Information for this article can be found under http://
dx.doi.org/10.1002/open.201600092.
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This is an open access article under the terms of the Creative Commons
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reproduction in any medium, provided the original work is properly
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sentative of H-type compounds with silver acetate and silver
2.2. Molecular Structures in the Solid State
perchlorate.
Compound 1 has already been reported,[76,77] but its crystal
structure is unknown. The molecular structures of com-
pounds 1, 2, and 4–7 have been determined by single-crystal
X-ray diffraction analysis and are shown in Figures 1–6, respec-
tively. Selected interatomic distances and angles are given in
the figure captions. Compound 1 crystallized in the triclinic
space group PÀ1. The unit cell of 1 contains two crystallo-
graphic independent molecules A and B, for which the intera-
tomic distances and angles differ only slightly. Consequently,
only molecule A is shown and a selection of its parameters is
2. Results and Discussion
2.1. Synthetic Aspects
According to the procedure reported in the literature,[76] the re-
action of lithium triphenylstannide, Ph3SnLi, with trichlorome-
thane, CHCl3, provides the methine-bridged tritin compound
HC(SnPh3)3, 1. In a modified procedure using sodium triphenyl-
stannide, Ph3SnNa, the yield obtained of 1 was similar. The sep-
aration of compound 1 from the unavoidable by-product hex-
aphenyldistannane, Ph3SnSnPh3, by both re-crystallization and
chromatography proved to be tedious. Consequently, the con-
tent of Ph3SnSnPh3 was estimated from a 119Sn NMR spectrum
of the crude reaction mixture. Then, the reaction mixture was
treated with an equimolar quantity of elemental iodine (I2) per
Ph3SnSnPh3, exclusively giving Ph3SnI, which in turn was trans-
ferred into poorly soluble triphenyltin fluoride, Ph3SnF, by stir-
ring the reaction mixture with aqueous potassium fluoride, KF.
The Ph3SnF was filtered, leaving a solution exclusively contain-
ing compound 1. The reaction of the latter with 3 molar equiv-
alents of I2 afforded tris(diphenyliodostannyl)methane,
HC(SnIPh2)3, 2. This compound was reacted with an excess of
potassium fluoride, KF, in a biphasic mixture CH2Cl2/H2O for
3 days to give the corresponding fluorine-substituted deriva-
tive HC(SnFPh2)3, 3. The corresponding organotin chloride de-
rivative HC(SnClPh2)3, 4, was obtained through the reaction of
compound 2 with an excess of silver chloride, AgCl. The treat-
ment of 2 with silver acetate, AgOAc, gave the corresponding
organotin acetate HC{Sn(OAc)Ph2}3, 5. The reaction of com-
pound 1 with 6 molar equivalents of elemental iodine provided
tris(phenyldiiodostannyl)methane HC(SnI2Ph)3, 6 (Scheme 2). In
Figure 1. General view (SHELXTL) of a molecule of compound 1 showing
30% probability displacement ellipsoids. Hydrogen atoms at the phenyl
rings are omitted for clarity. Selected interatomic distances (Š): Sn(1)–C(1)
2.160(4), Sn(1)–C(11) 2.153(4), Sn(1)–C(21) 2.156(4), Sn(1)–C(31) 2.147(4). Se-
lected interatomic angles (8): Sn(1)–C(1)–Sn(2) 114.49(17), Sn(1)–C(1)–Sn(3)
113.34(18), Sn(2)–C(1)–Sn(3) 114.53(19), C(1)–Sn(1)–C(11) 107.00(16), C(1)–
Sn(1)–C(21) 112.77(15), C(1)–Sn(1)–C(31) 112.36(16), C(11)–Sn(1)–C(21)
107.98(15), C(11)–Sn(1)–C(31) 111.00(16), C(21)–Sn(1)–C(31) 105.71(16).
Scheme 2. Synthesis of compounds 1–7.
a similar manner as described for the synthesis of 4, com-
pound 6 was converted through a reaction with AgCl into the
corresponding organotin chloride HC(SnCl2Ph)3, 7. The com-
pounds are colorless (1, 4, 5, and 7), slightly yellow (2), or
deep yellow (6) crystalline materials that are soluble in organic
solvents such as CH2Cl2, CHCl3, and THF. Compound 3 is an
amorphous solid that is almost insoluble in common organic
solvents.
Figure 2. General view (SHELXTL) of the two independent propeller-type
molecules of compound 2 showing 30% probability displacement ellipsoids
and clockwise (left) and anti-clockwise (right) orientation. Of the phenyl sub-
stituents only the Cipso-carbon atoms are shown. Selected interatomic distan-
ces (Š): Sn(1)–C(1) 2.176(9), Sn(1)–C(11) 2.136(5), Sn(1)–C(21) 2.150(4), Sn(1)–
I(1) 2.7708(11), Sn(1)–I(3) 4.0301(11), Sn(2)–C(1) 2.131(9), Sn(2)–C(41) 2.141(5),
Sn(2)–C(51) 2.139(4), Sn(2)–I(1) 3.8287(10), Sn(2)–I(2) 2.7534(10), Sn(3)–C(1)
2.158(10), Sn(3)–C(71) 2.146(5), Sn(3)–C(81) 2.141(5), Sn(3)–I(2) 4.0623(10),
Sn(3)–I(3) 2.7352(10). Selected interatomic angles (8): Sn(1)–C(1)–Sn(2)
110.9(4), Sn(1)–C(1)–Sn(3) 113.4(4), Sn(2)–C(1)–Sn(3) 116.1(4), C(1)–Sn(1)–C(11)
112.7(3), C(1)–Sn(1)–C(21) 115.7(3), C(11)–Sn(1)–C(21) 117.5(2), I(1)–Sn(1)–I(3)
174.17(3), I(1)–Sn(2)–I(2) 176.97(3), I(2)–Sn(3)–I(3) 168.84(3).
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Figure 3. General view (SHELXTL) of the two independent propeller-type
molecules of compound 4 showing 30% probability displacement ellipsoids
and clockwise (right) and anti-clockwise (left) orientation. Of the phenyl sub-
stituents only the Cipso-carbon atoms are shown. Selected interatomic distan-
ces (Š): Sn(1)–C(1) 2.120(7), Sn(1)–C(11) 2.146(4), Sn(1)–C(21) 2.120(4), Sn(1)–
Cl(1) 2.4205(19), Sn(1)–Cl(3) 3.418(2), Sn(2)–C(1) 2.152(6), Sn(2)–C(41)
2.135(4), Sn(2)–C(51) 2.144(3), Sn(2)–Cl(1) 3.386(2), Sn(2)–Cl(2) 2.414(2),
Sn(3)–C(1) 2.138(6), Sn(3)–C(71) 2.135(4), Sn(3)–C(81) 2.139(3), Sn(3)–Cl(2)
3.3871(19), Sn(3)–Cl(3) 2.4059(19), Sn(12)–Cl(11) 3.4639(19), Sn(13)–Cl(12)
3.3125(19). Selected interatomic angles (8): Sn(1)–C(1)–Sn(2) 112.0(3), Sn(1)–
C(1)–Sn(3) 114.7(3), Sn(2)–C(1)–Sn(3) 114.2(3), C(1)–Sn(1)–C(11) 124.3(2), C(1)–
Sn(1)–C(21) 119.4(2), C(11)–Sn(1)–C(21) 108.83(19), Cl(1)–Sn(1)–Cl(3) 164.11(6),
Cl(1)–Sn(2)–Cl(2) 165.18(6), Cl(2)–Sn(3)–Cl(3) 164.45(6).
Figure 5. General view (SHELXTL) of a molecule of compound 6 showing
30% probability displacement ellipsoids. The hydrogen atoms of the phenyl
substituents are omitted for clarity. Selected interatomic distances (Š): Sn(1)–
C(1) 2.145(5), Sn(1)–C(11) 2.125(5), Sn(1)–I(1) 2.6699(4), Sn(1)–I(4) 2.6670(5).
Selected interatomic angles (8): Sn(1)–C(1)–Sn(2) 114.7(2), Sn(1)–C(1)–Sn(3)
114.02(19), Sn(2)–C(1)–Sn(3) 114.0(2), C(1)–Sn(1)–C(11) 119.48(17), C(1)–Sn(1)–
I(1) 104.13(11), C(1)–Sn(1)–I(4) 107.48(13), I(1)–Sn(1)–I(4) 107.581(16), I(1)–
Sn(1)–C(11) 106.65(13), I(4)–Sn(1)–C(11) 110.78(14).
Figure 4. General view (SHELXTL) of a molecule of compound 5·3CH2Cl2
showing 30% probability displacement ellipsoids. Of the phenyl substituents
only the Cipso-carbon atoms are shown. The CH3 hydrogen atoms are omitted
for clarity. Selected interatomic distances (Š): Sn(1)–C(1) 2.1445(14), Sn(1)–
C(11) 2.135(3), Sn(1)–C(21) 2.143(3), Sn(1)–O(1) 2.235(2), Sn(1)–O(2A) 2.246(2),
C(2)–O(1) 1.262(3), C(2)–O(2) 1.255(4). Selected interatomic angles (8): Sn(1)–
C(1)–Sn(1 A) 114.26(11), O(1)–Sn(1)–O(2A) 167.02(8), O(1)–C(2)–O(2) 124.5(3).
Figure 6. General view (SHELXTL) of a molecule of compound 7 showing
30% probability displacement ellipsoids. The hydrogen atoms of the phenyl
substituents are omitted for clarity. Selected interatomic distances (Š): Sn(1)–
C(1) 2.128(4), Sn(1)–C(11) 2.104(4), Sn(1)–Cl(1) 2.3468(13), Sn(1)–Cl(3)
3.5950(14), Sn(1)–Cl(4) 2.3357(11). Selected interatomic angles (8): Sn(1)–
C(1)–Sn(2) 113.04(19), Sn(1)–C(1)–Sn(3) 113.73(19), Sn(2)–C(1)–Sn(3)
114.05(19), C(1)–Sn(1)–C(11) 129.83(16), C(1)–Sn(1)–Cl(4) 108.12(11), C(11)–
Sn(1)–Cl(4) 105.39(12), Cl(1)–Sn(1)–Cl(3) 171.38(4).
discussed. Figure S1 shows both molecules A and B. The Sn(1)
atom exhibits a distorted tetrahedral environment with angles
ranging between 105.71(16) [C(21)–Sn(1)–C(31)] and
112.77(15)8 [C(1)–Sn(1)–C(21)]. The environments about the
Sn(2) and Sn(3) atoms are similar and not discussed in detail.
As a result of steric constraint, the central C(1) atom shows an
even more distorted tetrahedral environment with SnÀCÀSn
angles ranging between 114.53(19) [Sn(2)–C(1)–Sn(3)] and
113.34(18)8 [Sn(1)–C(1)–Sn(3)].
Compound 2 crystallized in the orthorhombic space group
Pbca containing two crystallographically independent mole-
cules C and D per asymmetric unit. Each of the independent
tin atoms in 2 (molecule C) is [4+1]-coordinated by one iodine
and three carbon atoms, forming a distorted tetrahedron. A
second iodine atom approaches the central tin atom via a tetra-
hedral face at SnÀI, distances ranging between 4.0623(10)
[Sn(3)–I(2)] and 3.8287(10) Š [Sn(2)–I(1)] being slightly shorter
than the sum of the van der Waals radii[78a] of tin (2.20 Š) and
iodine (1.95–2.12 Š), and all fall in the range of the correspond-
ing SnÀI distance found in {[SnBr(C6H5)2(C28H20I)], 3.8835(5)}.[79a]
These interactions cause, in part, a slight lengthening, as com-
pared with the sum of the covalent radii[78b] of tin and iodine
(2.73 Š), with the other SnÀI distances ranging from 2.7352(10)
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[Sn(3)–I(3)] to 2.7708(11) Š [Sn(1)–I(1)]. They fall in the range of
the SnÀI distances for tetra- and [4+1]-coordinated triorgano-
tin iodides such as fc(SiMe2CH2)2Sn(I)CH2CH(CH2OC2H4OCH2)2
polymers, in which the carboxylate anions coordinate the tin
centers unisobidentate as well.[88]
The diorganotin dihalides 6 and 7 both crystallized in the
monoclinic space group P21/c, containing four molecules in
the unit cell. The structures resemble those of the triorganotin
halides 2 and 4 in that they are pairs of enantiomers of propel-
ler-type molecules. However, in contrast to the latter, the geo-
metric parameters within each pair of enantiomers are identic.
Each of the three crystallographically independent tin atoms in
both 6 and 7 is [4+1]-coordinated by two iodine and two
carbon (compound 6) or two chlorine and two carbon (com-
pound 7) atoms, forming distorted tetrahedra. A third iodine
(compound 6) or chlorine (compound 7) atom approaches the
corresponding tin center via a tetrahedral face at distances
ranging between 4.1665(5) (Sn3–I5) and 4.2288(5) (Sn2–I4), and
3.5950(14) (Sn1–Cl3) and 3.6476(13) (Sn2–Cl1), respectively.
These distances are shorter than the sums of the van der
Waals radii of the corresponding atoms.
(2.7309(4) Š),[80]
Ph2ISnCHCHCMe(tBu)OH
[2.7710(8),
2.763(1) Š],[81] and Ph2ISnCH2CH2CO2Me [2.811(2) Š][82]. The po-
sition of the experimentally determined geometry for each tin
atom along the path tetrahedron!trigonal bipyramid can be
quantified by the geometrical goodness DÆ(q).[79b] For com-
pound 2, the values fall in the range between 29.8 (Sn3) and
41.78 (Sn12), showing these to be closer to the tetrahedron
(ideal value 08) than to the trigonal bipyramid (ideal value 908).
Compound 4 crystallized in the triclinic space group PÀ1,
containing two crystallographic independent molecules E and
F per asymmetric unit. Like in 2, each of the independent tin
atoms in 4 is [4+1]-coordinated [range of geometrical good-
ness DÆ(q)[79b] 49.0 (Sn11)–54.68 (Sn1)] by one chlorine and
three carbon atoms, forming a distorted tetrahedron. A second
chlorine atom approaches the central tin atom via a tetrahedral
face at Sn–Cl distances ranging between 3.4639(19) [Sn(12)–
Cl(11)] and 3.3125(19) Š [Sn(13)–Cl(12)]. These distances are
shorter than the sum of the van der Waals radii[78a] of tin
(2.17 Š) and chlorine (1.75 Š) and are comparable with the
corresponding SnÀCl distances found in Me3SiCH2(Cl2)Sn(CH2)3-
Sn(Cl2)CH2SiMe3 [3.319(5) and 3.510(5) Š].[83] As a result of
these weak intramolecular Cl···Sn interactions (long distances),
the other SnÀCl distances ranging between 2.4205(19) Š
[Sn(1)–Cl(1)] and 2.4059(19) Š [Sn(3)–Cl(3), Sn(4)–Cl(4)] are
slightly longer than the corresponding distances in tetracoordi-
nated triorganotin chlorides such as [PhC(CH3)2CH2]3SnCl
[2.395(4) Š].[84] For both organotin halides 2 and 4, we deal
with pairs of enantiomers of propeller-type molecules, showing
clockwise and anti-clockwise orientation originating from weak
intramolecular halogen–tin interactions at distances just below
the sums of the van der Waals radii of the corresponding
atoms. The effect is more pronounced for organotin chloride 4
than organotin iodide 2. The interatomic distances and angles
differ slightly within the pairs of enantiomers. With caution,
this can be traced to some ionic character of the tin–halogen
bonds, which in turn allows interpretation of these structures
by a ligand close-packing model.[85]
2.3. Structures in Solution
The 119Sn NMR spectra of compounds 1, 2, 4, and 7 in CDCl3
show resonances at d À78, À70, À10, and À3, respectively,
which are comparable to those measured for the tetracoordi-
nated tetraorganotin compounds (Ph3Sn)2CH2 (d À79),[89]
(Ph2ISn)2CH2 (d À68),[89] (Ph2ClSnCH2)2 (d 2),[28k] and
(PhCl2Sn)2CH2 (d 8),[89] respectively. This is evidence that the tin
atoms in compounds 1, 2, 4, and 7 are four-coordinated with
distorted tetrahedral geometries, as observed in the solid
state. A 119Sn NMR spectrum of the organotin acetate 5 dis-
played a single resonance at d À206, indicating pentacoordi-
nation. A 119Sn NMR spectrum of compound 6 in CDCl3 dis-
played a resonance at d À262, which is low-frequency shifted
with respect to the 119Sn chemical shifts of analogous com-
pounds, having similar substituent patterns about the tin
atoms, such as (PhI2SnCH2)2 (d À169),[28k] and Me2SnI2 (d
À159).[90] The former resonance (d À262) is close to the 119Sn
chemical shifts reported for the hyper-coordinated organotin
compounds
PhI2SnCH2-[13]-crown-4
(d
À275)[91]
and
PhI2SnCH2SnI2-[13]-crown-4 [d À272, Sn(1)].[91] This observation
suggests that the tin atoms in 6 are penta-coordinated in
solution.
The triorganotin acetate 5, as its dichloromethane solvate
5·3CH2Cl2, crystallized in the trigonal space group RÀ3 contain-
ing six molecules in the unit cell. The one crystallographic in-
dependent Sn(1) atom is penta-coordinated by O(1) and O(2A)
occupying the axial and C(1), C(11), and C(21) occupying the
equatorial positions of a distorted trigonal bipyramid [geomet-
rical goodness DÆ(q)[79b] =88.98]. The distortion is best reflect-
ed by the O(1)–Sn(1)–O(2A) angle of 167.02(8)8, which deviates
by 12.988 from the ideal angle of 1808. The acetate anion coor-
dinates two neighboring tin atoms in an almost perfect isobi-
dentate mode at Sn(1)–O(1) and Sn(1)–O(2A) distances of
2.235(2) and 2.246(2) Š, respectively. To some extent, the
structure resembles that of the motif reported for
[{Me2Sn(O2CMe)}2O]2.[87] However, the latter is a diorganotin di-
carboxylate derivative and the acetate anions coordinate uni-
sobidentate with Sn–O distances between 2.24(1) and
2.38(2) Š. Triorganotin carboxylates are usually coordination
The solubility of compound 3 is too low in common organic
solvents to allow the measurement of its 119Sn, 19F, 13C, and
1H NMR spectra.
1
The H NMR spectra of compounds 1, 2, 4–7 show the ex-
pected singlets and coupling constants for the CH protons at d
1.46 [2J(1HÀ117/119Sn)=69 Hz, 1], 2.87 [2J(1HÀ117/119Sn)=72 Hz, 2],
3.15 [2J(1HÀ117/119Sn)=81 Hz, 4], 3.57 [2J(1HÀ117/119Sn)=66 Hz, 6],
2
and 3.04 [2J(1HÀ117Sn)=68 Hz, J(1HÀ119Sn)=76 Hz, 7].
The nonequivalence of the phenyl substituents in the orga-
notin acetate 5 is reflected by a 13C{1H} NMR spectrum showing
two resonances (d 142.0, 143.8 ppm) for the Ci and two reso-
nances (d 135.5, 136.0 ppm) for the Co carbon atoms.
An ESI–MS spectrum (negative mode) of compound 2
showed a major mass cluster centered at m/z 1338.4 assigned
to [HC(SnIPh2)3·I]À.
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2.4. Complexation Studies
The ability of compounds 2, 4, and 7 to complex anions was
studied. Thus, a 119Sn NMR spectrum (223.85 MHz) of com-
pound 2 in CD2Cl2 at room temperature, to which 1 molar
equivalent of tetraethylammonium fluoride (Et4NF·2H2O) had
been added, showed a single resonance at d À72 [2J(119SnÀ
117Sn)=230 Hz]. At T=193 K (149.26 MHz), two doublet reso-
nances are observed at d À55 [2J(119SnÀ117/119Sn)=367 Hz,
19
3J(119SnÀ F)=35 Hz, integral 30, SnIPh2] and d À163 [1J(119SnÀ
19F)=844 Hz, integral 60, n1/2 =95 Hz, HC(SnIPh2)2F]. Also pres-
ent is a singlet resonance at d À77 (integral 10, 2). A 19F NMR
spectrum (564.84 MHz) of the same sample at room tempera-
Figure 7. General view (SHELXTL) of the anion and cations of compound 8
showing 30% probability displacement ellipsoids. The hydrogen atoms of
the phenyl and ethyl substituents are omitted for clarity. Selected interatom-
ic distances (Š): Sn(1)–C(1) 2.160(10), Sn(1)–C(11) 2.169(6), Sn(1)–C(21)
2.141(6), Sn(1)–I(1) 2.8856(12), Sn(1)–F(10) 2.270(6), Sn(2)–I(2) 2.9150(12),
Sn(2)–F(10) 2.205(6), Sn(2)–I(3) 4.1206(14), Sn(3)–I(1) 4.0390(12), Sn(3)–I(3)
2.7360(12). Selected interatomic angles (8): Sn(1)–C(1)–Sn(2) 104.4(4), Sn(1)–
C(1)–Sn(3) 112.4(6), Sn(2)–C(1)–Sn(3) 120.5(5), Sn(1)–F(10)–Sn(2) 99.5(2), C(1)–
Sn(1)–C(11) 124.6(4), C(1)–Sn(1)–C(21) 121.6(4), C(11)–Sn(1)–C(21) 110.3(3),
I(1)–Sn(1)–F(10) 165.95(15), C(1)–Sn(2)–C(41) 128.2(4), C(1)–Sn(2)–C(51)
118.1(4), C(41)–Sn(2)–C(51) 111.4(3), I(2)–Sn(2)–F(10) 168.41(18), C(1)–Sn(3)–
C(71) 114.8(4), C(1)–Sn(3)–C(81) 117.2(4), C(1)–Sn(3)–I(3) 107.6(3), C(71)–
Sn(3)–C(81) 109.0(4), C(71)–Sn(3)–I(3) 106.9(2), C(81)–Sn(3)–I(3) 99.7(2), I(1)–
Sn(3)–I(3) 161.31(4).
ture displayed a broad singlet resonance at d À103 (n1/2
=
2018 Hz). At T=193 K (376.61 MHz), a doublet resonance
flanked with unresolved satellites was observed at d À104
1
[1J(19FÀ117/119Sn)=824 Hz, 3J(19FÀ H)=11 Hz]. The satellite-to-
signal-to-satellite integral ratio is approximately 14:72:14, un-
ambiguously proving the fluoride anion to be complexed by
19
two tin atoms. The 1J(119SnÀ F) and 1J(19FÀ117/119Sn) coupling
constants are comparable to the corresponding values report-
ed for [(Ph2ISn)2CH2·F] (780 Hz).[28 h]
The NMR data indicate SnÀF exchange processes (Scheme 3)
to be fast at room temperature and slow at low temperature
on the corresponding NMR timescales.
of 165.95(15)8 (Sn1) and 168.41(18)8 (Sn2), deviating from the
ideal angle of 1808. The tin atoms are displaced by 0.2325(8) Š
(Sn1) and 0.1898(8) Š (Sn2) from the trigonal planes defined by
C(1), C(11), C(21) (Sn1)/C(1), C(41), C(51) (Sn2) in the direction
of I(1) (Sn1) and I(2) (Sn2).
The Sn(3) atom is four-coordinated and shows a distorted
tetrahedral environment, with angles varying between 99.7(2)8
(C81–Sn3–I3) and 117.2(4)8 (C1–Sn3–C81). The distortion of the
tetrahedral environment is brought about by the I(1) and I(2)
atoms intramolecularly approaching the Sn(3) atoms via the
tetrahedral faces defined by C(1), C(71), C(81), and C(1), C(71),
I(3) at distances of 4.0390(12) and 4.1206(14) Š, respectively.
These distances are slightly shorter than the sum of the van
der Waals radii[78a] of tin (2.17 Š) and iodine (1.98 Š).
Scheme 3. Reaction of 2 with Et4NF·2H2O.
An ESI–MS spectrum in the positive mode of compound 2 in
CD3CN, to which 1 molar equivalent of Et4NF·2H2O had been
added, showed a mass cluster centered at m/z 865.1 that is as-
signed to {[(Ph2SnOH)2(Ph2Sn)]CH}+. In addition, there was
a less intense mass cluster centered at m/z 907.1, which corre-
sponds to {[(Ph2SnOH)2(Ph2SnF)]CH·Na}+. In the negative
mode, no tin-containing mass cluster was observed.
The coordination of the fluoride anion to the Sn(1) and Sn(2)
influences the Sn(1)–I(1) [2.8856(12)] and Sn(2)–I(2) [2.9150(12)]
bonds, which are lengthened in comparison with the corre-
sponding Sn(3)–I(3) bond [2.7360(12)] involving a tetracoordi-
nated tin atom. It exceeds the sum of the covalent radii of Sn
(1.40 Š) and I (1.33 Š).[78b]
The 119Sn NMR spectrum of compound 4 in CDCl3 to which
1 molar equivalent of tetraphenylphosphonium chloride,
Ph4PCl, had been added, showed a single resonance at d À98,
which is displaced by 88 ppm to low frequency with respect to
the chemical shift of the parent compound 4 (d À10). This
result is interpreted in terms of the formation of the organo-
chloridostannate complex Ph4P[HC(SnClPh2)3·Cl] (9), in which all
three tin atoms are equivalent on the 119Sn NMR timescale. The
complex was isolated from the reaction mixture as its dichloro-
methane solvate 9·1/3CH2Cl2, as colorless crystalline material
The
formation
of
the
organostannate
complex
NEt4[HC(SnIPh2)3·F] (8) was confirmed by X-ray diffraction analy-
sis. The molecular structure of the anion of 8 is shown in
Figure 7. Selected interatomic distances and angles are given
in the figure caption. The molecular structure of 8 shows that
the fluoride anion is chelated by two tin atoms to form a four-
membered CSn2F ring. The Sn(1) and Sn(2) atoms in com-
pound 8 are pentacoordinated and each exhibit a distorted
trigonal bipyramidal environment [geometrical goodness
DÆ(q)[79b] =67.48 (Sn1) and 76.18 (Sn2)] with C(1), C(11), and
C(21) (Sn1) and C(1), C(41), and C(51) (Sn2) occupying the
equatorial positions and F(10) and I(1) (Sn1), and F(10) and I(2)
(Sn2) occupying the axial positions. The distortion is expressed
by the F(10)–Sn(1)–I(1) (Sn1) and F(10)–Sn(2)–I(2) (Sn2) angles
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sitions and Cl(3) and Cl(10) occupying the axial positions. The
distortion is best reflected in the Cl(3)–Sn(3)–Cl(10) angle of
167.29(5)8, which deviates from the ideal angle of 1808. The
Sn(3) atom is displaced by 0.0138(4) Š from the trigonal plane
in the direction of Cl(10). The Sn(1) and Sn(2) atoms each ex-
hibit a distorted tetrahedral environment, with angles varying
between 99.52(10)8 (C21–Sn1–Cl1) and 120.80(17)8 (C1–Sn1–
C21) (Sn1), and 96.14(11)8 (C41–Sn2–Cl2) and 133.00(17)8 (C1–
Sn2–C51) (Sn2). The distortion from the ideal geometry is
mainly the result of the Cl(3) and Cl(10) atoms intramolecularly
approaching the Sn(2) and Sn(1) atoms at distances of
2.9397(14) and 3.4637(16) Š, respectively. These distances are
shorter than the sum of the van der Waals radii[78a] of tin
(2.17 Š) and Cl (1.75 Š), and render the corresponding tin
atoms [4+1]-coordinated. The Sn(2)–Cl(2) [2.4473(15) Š] and
Sn(1)–Cl(1) [2.3962(16) Š] distances reflect the different extent
of these [4+1]-coordinations, as do the geometrical goodness
DÆ(q)[79b] values of 40.08 for Sn(1) and 62.58 for Sn(2). The
latter distance is close to the corresponding distances in
tetra-coordinated triorganotin chlorides such as cyclo-
MeClSn(CH2SiMe2CH2)2SnClMe [Sn(1)–Cl(1) 2.3841(11) Š].[75]
They exceed the sum of the covalent radii[78b] of tin and chlor-
ine by 0.2407 and 0.196 Š, respectively.
Scheme 4. Reaction of 4 with Ph4PCl.
(Scheme 4). The formation of complex 9 is further supported
1
1
by H NMR spectroscopy and ESI–MS. The H NMR spectrum of
a solution of compound 9 in CDCl3 showed that the signal of
the methine (CH) proton is shifted to low frequency by
0.35 ppm. An ESI–MS mass spectrum of compound 9 in the
negative mode showed a mass cluster centered at m/z 729.9,
which is assigned to [HC(SnClPh2)3·Cl]À. No tin-containing mass
cluster was observed in an ESI–MS in the positive mode.
The molecular structure of the anion of 9·1/3CH2Cl2 is
shown in Figure 8. Selected interatomic distances and angles
are collected in the figure caption. The molecular structure of
9 shows that the chloride anion bridges the Sn(2) and Sn(3)
atoms non-symmetrically at Sn(2)–Cl(3) and Sn(3)–Cl(3) distan-
ces of 2.9397(14) and 2.6307(14) Š, respectively. The Sn(3)
atom is pentacoordinated and exhibits a distorted trigonal bi-
The 119Sn NMR spectrum of a solution of compound 7 in
CD2Cl2, to which 2 molar equivalents of Ph4PCl had been
added, showed a single resonance at d À248 that is shifted by
245 ppm to lower frequency as compared to 7, and that refers
to the formation of the organochloridostannate complex
(Ph4P)2[HC(SnCl2Ph)3·2Cl] (10) (Scheme 5). The latter was isolat-
pyramidal environment [geometrical goodness DÆ(q)[79b]
=
88.48] with C(1), C(71), and C(81) occupying the equatorial po-
Scheme 5. Reaction of 7 with Ph4PCl.
ed from the reaction mixture as colorless crystalline material.
Further experimental support for the formation of 10 stems
1
from the H NMR spectroscopy and ESI–MS. A 1H NMR spec-
trum of a solution of compound 10 in CD2Cl2 showed that the
signal of the methine (CH) proton is shifted to a higher fre-
quency by 1.31 ppm. The displacement of the chemical shift of
the methine proton in 10 to higher frequency contrasts well
with the low-frequency chemical shift observed for 9. An ESI–
MS mass spectrum of compound 10 in the negative mode
showed a mass cluster centered at m/z 848.6 that is assigned
to the anion of 10.
Compound 10 crystallized in the triclinic space group PÀ1
with two molecules per unit cell. The molecular structure of
the anion of 10 is shown in Figure 9. Selected interatomic dis-
tances and angles are collected in the figure caption. It con-
sists of a centrosymmetric doubly intramolecularly chlorido-
bridged organostannate anion and two tetraphenylphos-
Figure 8. General view (SHELXTL) of the anion and cation of 9·1/3CH2Cl2
showing 30% probability displacement ellipsoids. The hydrogen atoms at
the phenyl substituents are omitted for clarity. Selected interatomic distan-
ces (Š): Sn(1)–C(1) 2.136(5), Sn(1)–C(11) 2.126(3), Sn(1)–C(21) 2.143(2), Sn(1)–
Cl(1) 2.3962(16), Sn(1)–Cl(10) 3.4644(16), Sn(2)–Cl(2) 2.4473(15), Sn(2)–Cl(3)
2.9397(14), Sn(3)–Cl(3) 2.6307(14), Sn(3)–Cl(10) 2.5860(15). Selected intera-
tomic angles (8): Sn(1)–C(1)–Sn(2) 118.9(3), Sn(1)–C(1)–Sn(3) 111.2(2), Sn(2)–
C(1)–Sn(3) 115.2(2), Sn(2)–Cl(3)–Sn(3) 80.63(4), C(1)–Sn(1)–C(11) 113.73(18),
C(1)–Sn(1)–C(21) 120.80(17), C(1)–Sn(1)–Cl(1) 101.99(16), C(11)–Sn(1)–C(21)
112.35(15), C(11)–Sn(1)–Cl(1) 105.37(14), C(21)–Sn(1)–Cl(1) 99.52(10), Cl(1)–
Sn(1)–Cl(10) 159.83(5), C(1)–Sn(2)–C(41) 112.24(18), C(1)–Sn(2)–C(51)
133.00(17), C(41)–Sn(2)–C(51) 109.52(14), Cl(2)–Sn(2)–Cl(3) 173.57(5), C(1)–
Sn(3)–C(71) 119.38(18), C(1)–Sn(3)-C(81) 126.11(17), C(1)–Sn(3)–Cl(3)
84.29(15), C(1)–Sn(3)–Cl(10) 83.16(15), C(71)–Sn(3)–C(81) 114.50(15), C(71)–
Sn(3)–Cl(3) 90.89(13), C(71)–Sn(3)–Cl(10) 93.51(13), C(81)–Sn(3)–Cl(3) 94.05(9),
C(81)–Sn(3)–Cl(10) 94.96(9), Cl(3)–Sn(3)–Cl(10) 167.29(5).
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Sn(1)–Cl(1) [2.366(4) Š] and Sn(1)–Cl(4) [2.382(3) Š] distances
are almost the same and slightly shorter than the Sn(1)–Cl(1)
and Sn(2)–Cl(2) distances in 9.
2.5. Reaction of HC(SnIPh2)3 with AgClO4
The reaction under non-inert conditions of the triorganotin
iodide derivative 2 with silver perchlorate in a 1:3 molar ratio
gave a crude reaction mixture, a 119Sn NMR spectrum of which
showed five resonances at d À69 [2J(119SnÀ117Sn)=236 Hz, inte-
gral 2.0, 2], À76 [2J(119SnÀ117/119Sn)=297/310 Hz, 2J(119SnÀ
13
13
117Sn)=232 Hz, 1J(119SnÀ Ci)=591 Hz, 2J(119SnÀ Co)=52 Hz,
3J(119SnÀ Cm)=69 Hz, integral 10.2, signal a], À83 [2J(119SnÀ
13
117/119Sn)=270/283 Hz, integral 1.0, signal b], À228 [2J(119SnÀ
117/119Sn)=297/310 Hz, integral 5.7, signal c], and À244
[2J(119SnÀ117/119Sn)=271/283 Hz, 2J(119SnÀ117Sn)=370 Hz, inte-
gral 2.9, signal d]. From the 2J(119SnÀ117/119Sn) coupling con-
stants and integral ratio, we conclude that signals a and
c belong to one compound that contains three tin atoms, two
of which are chemically identical. The identity of this com-
pound was, however, not established. Signals b and d seem
also to belong to one compound (from coupling arguments),
but the integral ratio of almost 1:3 disfavors this view. From
the reaction mixture, the partially hydrolyzed organotin(IV) per-
chlorate derivative 11 was obtained as a colorless crystalline
material (Scheme 6) that, once crystallized, showed rather poor
solubility. Consequently, no NMR spectra were recorded.
Figure 9. General view (SHELXTL) of the anion and cations of compound 10
showing 30% probability displacement ellipsoids. The hydrogen atoms at
the phenyl substituents are omitted for clarity. Selected interatomic distan-
ces (Š): Sn(1)–C(1) 2.114(14), Sn(1)–C(11) 1.982(13), Sn(1)–Cl(1) 2.366(4),
Sn(1)–Cl(4) 2.382(3), Sn(1)–Cl(5) 3.536(3), Sn(1)–Cl(6) 3.218(3), Sn(2)–C(1)
2.149(11), Sn(2)–C(21) 2.124(6), Sn(2)–Cl(2) 2.453(3), Sn(2)–Cl(5) 2.435(3),
Sn(2)–Cl(10) 2.686(3), Sn(2)–Cl(20) 2.894(3), Sn(3)–C(1) 2.111(14), Sn(3)–C(31)
2.198(8), Sn(3)–Cl(3) 2.408(3), Sn(3)–Cl(6) 2.481(3), Sn(3)–Cl(10) 2.868(3),
Sn(3)–Cl(20) 2.713(3). Selected interatomic angles (8): Sn(1)–C(1)–Sn(2)
113.6(5), Sn(1)–C(1)–Sn(3) 115.7(6), Sn(2)–C(1)–Sn(3) 106.2(6), C(1)–Sn(1)–Cl(1)
108.2(3), C(1)–Sn(1)–C(11) 136.7(6), C(1)–Sn(1)–Cl(4) 105.2(4), Cl(1)–Sn(1)–Cl(4)
92.60(15), Cl(1)–Sn(1)–C(11) 98.9(5), Cl(4)–Sn(1)–C(11) 106.6(5), C(1)–Sn(2)–
C(21) 156.8(4), Cl(2)–Sn(2)–Cl(10) 175.47(10), Cl(5)–Sn(2)–Cl(20) 169.96(10),
C(1)–Sn(3)–C(31) 157.1(4), Cl(3)–Sn(3)–Cl(10) 175.91(14), Cl(6)–Sn(3)–Cl(20)
170.06(10).
phonium cations, and resembles that of (Et4N)2[cyclo-
Cl2Sn(CH2SiMe2CH2)2SnCl2·2Cl].[75]
The Sn(2) and Sn(3) tin atoms are hexa-coordinated and ex-
hibit each a distorted octahedral all-trans SnC2Cl4 environment
with C(1)–Sn(2)–C(21), Cl(2)–Sn(2)–Cl(10), Cl(5)–Sn(2)–Cl(20),
C(1)–Sn(3)–C(31), Cl(3)–Sn(3)–Cl(10), and Cl(6)–Sn(3)–Cl(20)
angles of 156.8(4), 175.47(10), 169.96(10), 157.1(4), 175.91(14),
and 170.06(10)8, respectively. The chlorido bridges are unsym-
metrical with Sn(2)–Cl(10), Sn(2)–Cl(20), Sn(3)–Cl(10), and
Sn(3)–Cl(20) distances of 2.686(3), 2.894(3), 2.868(3), and
2.713(3) Š, respectively. The Sn(2)–Cl(2), Sn(2)–Cl(5), Sn(3)–Cl(3),
and Sn(3)–Cl(6) distances of 2.453(3), 2.435(3), 2.408(3), and
2.481(3) are comparable with the corresponding distances
Scheme 6. Reaction of 2 with AgClO4.
The formation of 11 under the experimental conditions em-
ployed can, with caution, be rationalized by hydrolysis of a tin
perchlorate function giving perchloric acid, which in turn
cleaves a SnÀCPhenyl bond.
The molecular structure of compound 11 is shown in
Figure 10. Selected interatomic distances and angles are col-
lected in the figure caption.
in
(Et4N)2[cyclo-Cl2Sn(CH2SiMe2CH2)2SnCl2·2Cl]
[2.4735(6),
Compound 11 crystallized in the orthorhombic space group
Pbca with four molecules in the unit cell. It is a centrosymmet-
ric dimer consisting of two CSn3 moieties. The Sn(2) and Sn(3)
atoms are pentacoordinated and each exhibits a distorted
trigonal bipyramidal environment [geometrical goodness
DÆ(q)[79b] =79.98 (Sn2) and 85.88 (Sn3) with C(1), C(21), and
C(31) (Sn(2)] with C(1), C(41), and C(51) (Sn3) occupying the
equatorial positions and O(1) and O(11) (Sn2), and O(12) and
O(15) (Sn3) occupying the axial positions. The Sn(2) and Sn(3)
2.4906(5) Š].[75] The situation at Sn(2) and Sn(3) can be seen as
a model for SN3 substitution pathways at SnC2Cl2 moieties, as
reported by Britton and Dunitz.[86] The Sn(1) atom is four-coor-
dinated and shows a distorted tetrahedral environment, with
angles varying between 98.9(5)8 [Cl(1)–Sn(1)–C(11)] and
136.7(6)8 [C(1)–Sn(1)–C(11)]. The distortion is expressed by the
Cl(5) and Cl(6) atoms intramolecularly approaching the Sn(1)
atom at distances of 3.536(3) and 3.218(3) Š, respectively. The
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and/or intramolecular interaction with the remaining halogen
substituents. As it is nicely shown for the chloridostannate
complex 9, as compared with the corresponding host com-
pound 4, the strength of the intramolecular Sn–Cl!Sn interac-
tion is enhanced by the incoming chloride anion (guest). The
acetate-substituted derivative HC{Sn(OAc)Ph2}3 shows a highly
symmetric structure in the solid state that is retained in solu-
tion. The replacement of the acetate moiety by other poten-
tially bridging substituents such diorganophosphinate is in
progress. The isolation of [HC{Sn(ClO4)2Ph2}2Sn(OH)2Ph]2, al-
though achieved by serendipity only, illustrates the potential
of the tris(organostannyl)methane derivatives for the synthesis
of unprecedented organotin oxoclusters. Examples for this
have been presented at the 14th International Symposium on
Inorganic Ring Systems (IRIS14, Book of Abstracts A27) and de-
tails will be reported in a forthcoming paper.
Figure 10. General view (SHELXTL) of a molecule of 11 showing 30% proba-
bility displacement ellipsoids. Of the phenyl substituents only the Cipso
-
carbon atoms are shown. Selected interatomic distances (Š): Sn(1)–C(1)
2.122(7), Sn(1)–C(11) 2.123(8), Sn(1)–O(1) 2.155(5), Sn(1)–O(10) 2.042(5),
Sn(1)–O(10 A) 2.181(5), Sn(2)–C(1) 2.153(7), Sn(2)–C(41) 2.134(7), Sn(2)–C(51)
2.114(9), Sn(2)–O(1) 2.124(5), Sn(2)–O(21) 2.503(5), Sn(3)–C(1) 2.125(7), Sn(3)–
C(71) 2.112(8), Sn(3)–C(81) 2.124(7), Sn(3)–O(22) 2.440(6), Sn(3)–O(25)
2.304(5), O(1)···O(24B) 2.931(7), O(10)···O(28 A) 2.789(9). Selected interatomic
angles (8): Sn(1)–C(1)–Sn(2) 100.9(3), Sn(1)–C(1)–Sn(3) 116.4(3), Sn(1)–O(1)–
Sn(2) 100.8(2), Sn(1)–O(10)–Sn(1 A) 109.4(2), Sn(2)–C(1)–Sn(3) 126.1(3), C(1)–
Sn(1)–C(11) 144.6(3), C(1)–Sn(1)–O(10) 106.2(3), C(11)–Sn(1)–O(10) 108.8(3),
O(1)–Sn(1)–O(10 A) 159.7(2), C(1)–Sn(2)–C(41) 122.8(3), C(1)–Sn(2)–C(51)
116.9(3), C(41)–Sn(2)–C(51) 119.4(3), O(1)–Sn(2)–O(21) 165.64(18), C(1)–Sn(3)–
C(71) 126.1(3), C(1)–Sn(3)–C(81) 112.7(3), C(71)–Sn(3)–C(81) 121.1(3), O(22)–
Sn(3)–O(25) 172.86(18). Symmetry codes: A) Àx+1, Ày+2, -z+1; B) Àx+1/
2, y+1/2, z.
Experimental Section
General Methods
Where necessary, reactions were carried out under an inert argon
atmosphere using standard Schlenk techniques. The solvents were
dried by standard methods and freshly distilled before use.
Et4NF·2H2O, Ph4PCl, AgCl, and KF were commercially available.
The NMR spectra were, unless otherwise stated, recorded at ambi-
ent temperature on Bruker DPX 300, DRX 400, DRX 500, AVANCE III
HD-400, AVANCE III HD-600 and AVANCE III HD-700 spectrometers.
The chemical shifts d are given in ppm and referenced to tetrame-
thylstannane (119Sn), and trichlorofluoromethane (19F) and tetrame-
thylsilane (1H, 13C). Electrospray mass spectroscopy (ESI–MS) was re-
corded on a Thermoquest–Finnigan instrument using CH3CN as
the mobile phase. The samples were introduced as solution in
CH3CN through a syringe pump operating at 0.5 mLminÀ1. The ca-
pillary voltage was 4.5 kV, whereas the cone skimmer voltage was
varied between 50 and 250 kV. Identification of the expected ions
was assisted by comparison of experimental and calculated isotope
distribution patterns. The m/z values reported correspond to those
of the most intense peak in the corresponding isotope pattern. Ele-
mental analyses were performed on a LECO-CHNS-932 analyzer.
Melting points were determined using a Büchi Melting Point M-
560. IR spectra were recorded on a PerkinElmer FTIR spectrometer.
atoms are displaced by 0.1161(5) and 0.0461 (6) Š from the
trigonal plane in the direction of O(2) and O(15), respectively.
The Sn(1) atom is pentacoordinated as well, but its geometry
is best seen as a square pyramid with C(1), C(11), O(1), and
O(10A) occupying the equatorial positions and O(10) occupy-
ing the apical position. The structure is stabilized by a non-
symmetric intramolecular O(10)–H(10)···O(28A) hydrogen
bridge at an O(10)···O(28A) distance of 2.789(9) Š. In addition,
there is an intermolecular O(1)–H(1)···O(24B) hydrogen bridge
at an O(1)···O(24B) distance of 2.931(7) Š.
Crystallography
3. Conclusions
Intensity data for all crystals were collected on an XcaliburS CCD
diffractometer (Oxford Diffraction) using Mo Ka radiation at 173 K.
The structures were solved with direct methods using SHELXS-
2014/7,[92] and refinements were carried out against F2 by using
SHELXL-2014/7.[92] The CÀH hydrogen atoms were positioned with
idealized geometry and refined using a riding model. All non-hy-
drogen atoms were refined using anisotropic displacement
parameters.
A series of tris(organostannyl)methanes and their chloride and
fluoride complexes has been synthesized and completely char-
acterized. In the solid state, the halogen-substituted derivatives
HC(SnXPh2)3 (X=Cl, I) show propeller-type structures with
clockwise and anti-clockwise orientation of the X!Sn coordi-
nation. These compounds give 1:1-complexes with chloride
and fluoride anions, respectively. No 1:2 or 1:3 complexes were
obtained, however. On the other hand, the hexachlorido-sub-
stituted derivative HC(SnCl2Ph)3 complexes two chloride
anions. All of these compounds [HC(SnXPh2)3 (X=Cl, I) and
HC(SnCl2Ph)3] have in common that they act as bicentric rather
than tricentric Lewis acids. The third tin atoms in each of these
derivatives appear to be satisfied by either steric protection
The nitrogen atoms N1A and N1B in compound 8 are half occu-
pied for symmetry reasons. The associated ethyl groups C91 to
C98 are affected by disorder and refined by a split model over two
positions (occupancy values (50/50).
The disordered electron density of a non-coordinating solvent mol-
ecule of compound 9 was modelled by the SQUEEZE routine of
the program Platon[93] to improve the main part of the structure.
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1
13
2
13
3
13
In compound 10, there are short non-bonding inter H···H contacts
(H14B···H36A, 1.60 Š; H32A···H95B, 1.36 Š), which can be explained
by packing effects. Several phenyl groups of compound 10 are af-
fected by disorder and refined by a split model over two positions
(C11 to C16, 50/50; C41 to C46, 60/40; C51 to C56, 60/40; C71 to
C76, 50/50; C81 to C86, 60/40; C91 to C96, 65/35).[94]
278 Hz, J(119SnÀ C) 509 Hz, J(119SnÀ C) 38 Hz, J(119SnÀ C) 51 Hz].
Anal. calcd for C55H46Sn3 (1062.99): C 62.1; H 4.4. Found: C 62.0; H
4.6.
For decimal rounding of numerical parameters and standard uncer-
tainty (su) values, the rules of IUCr have been employed.[95]
Synthesis of Tris(iodidodiphenylstannyl)methane
HC(SnIPh2)3 (2)
Over a period of 3 h, elemental iodine (96 mg, 0.378 mmol) was
added in small portions at 08C to a stirred solution of 1 (134 mg,
0.126 mmol) in CH2Cl2. Stirring was continued and the reaction
mixture was warmed to room temperature overnight. Dichlorome-
thane and iodobenzene were removed in vacuo (10À3 mmHg) to
afford a slightly yellow solid. Recrystallization from CH2Cl2/hexane
or ethanol gave 125 mg (82%) of pure 2 as colorless crystals, mp
1078C.
Synthesis of Tris(triphenylstannyl)methane HC(SnPh3)3 (1)
Method A
To a solution of Ph3SnCl (3 g, 7.8 mmol) in THF (100 mL) was added
lithium (0.54 g, 78 mmol), and the mixture was stirred overnight.
After filtration of the excess of lithium, chloroform (21 mL,
26 mmol) was added dropwise at room temperature. The mixture
was stirred for 3 h. The solvent was evaporated and the residue
was heated at reflux in hexane. The mixture was hot filtered and
allowed to stand overnight at room temperature. The solid materi-
al that had been deposited was separated and recrystallized sever-
al times from hexane to afford 0.53 g (19%) of pure 1 as colorless
crystals, mp 1398C.
2
1H NMR (CDCl3, 400.25 MHz, 294 K): d 2.87 [s, 1 H, J(1HÀ117/119Sn)=
13
70/72 Hz, 1J(1HÀ C)=141 Hz, CH], 7.29–7.54 (complex pattern,
30H, Ph). 13C{1H} NMR (CDCl3, 100.64 MHz, 294 K): d: À0.3 [1J(13CÀ
117/119Sn)=154/161 Hz, CH], 128.7 [3J(13CÀ117/119Sn)=65/67 Hz, Cm],
130.0 [4J(13CÀ117/119Sn)=14 Hz, Cp], 136.6 [2J(13CÀ117/119Sn)=51 Hz,
Co], 138.2 [1J(13CÀ117/119Sn)=564/590 Hz, 3J(13CÀ117/119Sn)=7 Hz, Ci].
119Sn{1H} NMR (CHCl3, 111.92 MHz, 298 K): d À70 [2J(119SnÀ117Sn)=
234 Hz]. Anal. calcd for C37H31I3Sn3 (1212.5): C 36.7; H 2.6. Found: C
36.6; H 2.7.
Method B
To a solution of Ph3SnCl (3.00 g, 7.78 mmol, 3.0 equiv) in THF
(150 mL) were added metallic sodium (0.43 g, 18.68 mmol,
7.2 equiv) and a catalytic amount of naphthalene. The mixture was
stirred at room temperature for 5 days, during which its color
changed to deep black. Activation by ultrasound (45 min) and ad-
dition of a further catalytic amount of naphthalene accelerated the
process. After the solution had been separated from non-reacted
sodium, CHCl3 (0.21 mL, 2.59 mmol, 1.0 equiv) was added dropwise
at À708C under magnetic stirring. Overnight, the reaction mixture
was warmed to room temperature followed by evaporation of the
solvent in vacuo. To the residue thus obtained, diethyl ether
(100 mL) was added and it was washed with distilled water (3”
50 mL) in order to remove the sodium chloride. The organic phase
was dried over MgSO4. The latter was separated by filtration and
the solvent of the filtrate was removed in vacuo, giving an amor-
phous solid material that was recrystallized from iso-hexane to give
a crystalline solid. A 119Sn NMR spectrum of a solution of this mate-
rial in CDCl3 revealed two resonances at d À78 (integral 85, 1) and
d À144 (integral 15, Ph3SnSnPh3). To remove the by-product
Ph3SnSnPh3, elemental iodine (0.042 g, 0.166 mmol, 1.1 equiv with
respect to Ph3SnSnPh3) was added in small portions to a magneti-
cally stirred solution of the crystalline solid (0.73 g) in CH2Cl2
(20 mL) at À208C. The reaction mixture was slowly warmed to
room temperature, which was followed by addition of an aqueous
solution of KF. Stirring this two-phase mixture for 3 h caused pre-
cipitation of Ph3SnF, which was separated by filtration. The organic
layer was separated, washed with distilled water, dried over
MgSO4, and then filtrated. Evaporation of the solvent in vacuo
gave compound 1 (0.49 g, 0.46 mmol, 18%) as a crystalline
material.
Synthesis of Tris(fluoridodiphenylstannyl)methane
HC(SnFPh2)3 (3)
A solution of 2 (200 mg, 0.165 mmol) in CH2Cl2 (25 mL) was mixed
with a solution of KF (96 mg, 1.65 mmol) in water (20 mL). The bi-
phasic mixture was stirred at room temperature for 3 days. The or-
ganic phase was then separated, dried over MgSO4, and filtered.
Removing the solvent in vacuo afforded 90 mg (61%) of 3 as amor-
phous solid material of mp 2648C that was almost insoluble in or-
ganic solvents. Consequently, no NMR spectra were recorded.
Anal. calcd for C37H31F3Sn3 (888.8): C 50.0; H 3.5. Found: C 48.0; H
3.8.
Synthesis of Tris(chloridodiphenylstannyl)methane
HC(SnClPh2)3 (4)
To a solution of 2 (150 mg, 0.12 mmol) in CH2Cl2 (20 mL) an excess
of silver chloride (180 mg, 1.24 mmol) was added. The resulting
mixture was stirred at room temperature in the dark for 14 days.
The AgI that had formed and the non-reacted AgCl were removed
by filtration. The solvent of the filtrate was evaporated in vacuo
(10À3 mmHg) to afford a white solid. Recrystallization of the latter
from CH2Cl2/n-hexane gave 83 mg (74%) of pure 4 as colorless
crystals, mp 1608C.
2
1H NMR (CDCl3, 300.13 MHz, 295 K): d 3.15 [s, 1H, J(1HÀ117/119Sn)=
2
1H NMR (CDCl3, 400.25 MHz, 294 K): d 1.48 [s, 1H, J(1HÀ117/119Sn)=
72 Hz, CH], 7.32–7.65 (complex pattern, 30H, Ph). 13C{1H} NMR
(CDCl3, 75.47 MHz, 296 K): d: 25.3 (CH), 128.9 [3J(13CÀ117/119Sn)=71/
86 Hz, Cm], 130.3 [4J(13CÀ117/119Sn=16 Hz, Cp)], 136.3 [2J(13CÀ
117/119Sn)=54 Hz, Co], 138.9 (Ci). No 1J(13CÀ117/119Sn) coupling con-
stants were obtained. 119Sn{1H} NMR (CDCl3, 149.26 MHz, 294 K): d
À9 [2J(119SnÀ117Sn)=203 Hz]. Anal. calcd for C37H31Cl3Sn3 (938.13): C
47.4; H 3.3. Found: C 47.5; H 3.7.
13
67/70 Hz, 1J(1HÀ C)=138 Hz, CH], 6.93–7.50 (complex pattern,
45H, Ph). 13C{1H} NMR (CDCl3, 150.94 MHz, 294 K): d: À21.2 [1J(13CÀ
117/119Sn)=183/190 Hz, CH], 128.1 [3J(13CÀ117/119Sn)=51 Hz, Cm],
128.5 [4J(13CÀ117/119Sn)=11 Hz, Cp], 137.2 [2J(13CÀ117/119Sn)=38 Hz,
Co], 140.2 [1J(13CÀ117/119Sn)=486/511 Hz, 3J(13CÀ117/119Sn)=11 Hz, Ci].
119Sn{1H} NMR (CDCl3, 149.26 MHz, 298 K): d À78 [2J(119SnÀ117Sn)=
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Synthesis of HC[Sn(OAc)Ph2]3 (5)
Synthesis of Et4N[(HC(SnIPh2)3·F] (8)
3 molar equivalents of silver acetate (41 mg, 0.24 mmol) were
added to a solution of 2 (99 mg, 0.08 mmol) in CH2Cl2 (15 mL). The
resulting mixture was stirred at room temperature in the dark for
2 days. The AgI formed was removed by filtration. The filtrate was
kept at À58C for several days to give 41 mg (51%) of pure 5 as
colorless crystals of its dichloromethane solvate 5·3CH2Cl2, mp
1668C.
Tetraethylammonium fluoride dihydrate (8 mg, 0.05 mmol) was
added to a solution of 2 (58 mg, 0.05 mmol) in dichloromethane
and the mixture was stirred at room temperature overnight. The
solvent was evaporated in vacuo to afford a white solid. Recrystalli-
zation of the latter from CH3CN gave 26 mg (40%) of pure 8 as col-
orless crystals mp=1808C.
Anal. calcd for C45H51FI3NSn3 (1361.64): C 39.7; H 3.8; N 1.0 Found:
C 39.5; H 4.0; N 1.2.
1H NMR (CDCl3, 700.19 MHz, 298 K): d 1.71 (s, 9H, CH3), 2.42 [s, 1H,
2J(1HÀ117/119Sn)=91 Hz], 7.22–7.90 (complex pattern, 30H, Ph).
13C{1H} NMR (CDCl3, 176.06 MHz, 296 K): d: 4.3 [1J(13CÀ117/119Sn)=
349/366 Hz, CH], 24.5 (CH3COO), 128.3 [3J(13C–117/119Sn)=76 Hz, Cm],
129.2 (Cp), 135.6 [2J(13CÀ117/119Sn)=63 Hz, Co], 136.0 [2J(13CÀ
117/119Sn)=46 Hz, Co], 142.0(Ci), 143.8 (Ci), 182.4 (CH3COO). 119Sn{1H}
NMR (CDCl3, 223.85 MHz, 294 K): d À206 [2J(119SnÀ117Sn)=199 Hz].
Anal. calcd for C46H46Cl6O6Sn3 (1263.70): C 43.7; H 3.7. Found:
C43.8; H 3.8
The NMR spectroscopic data given below were obtained from a so-
lution of compound 2, to which had been added 1 molar equiva-
lent of NEt4F·2H2O.
19F NMR (CD2Cl2, 376.61 MHz, 193 K) d À104 [d, 1J(19FÀ117/119Sn)=
1
824 Hz, 3J(19FÀ H)=11 Hz]. 19F NMR (CD2Cl2, 564.84 MHz, 298 K) d
À103 (n1/2 2018 Hz). 119Sn{1H} NMR (CD2Cl2, 149.26 MHz, 193 K): d
19
À163 [d, 1J(119SnÀ F)=844 Hz, 8], À77 (2), À55 [d, 2J(119SnÀ
19
117/119Sn)=367 Hz, 3J(119SnÀ F)=35 Hz, 8]. 119Sn{1H} NMR (CD2Cl2,
223.85 MHz, 298 K): d À72 (2).
Synthesis of Tris(diiodidophenylstannyl)methane
HC(SnI2Ph)3 (6)
Synthesis of PPh4[(HC(SnClPh2)3·Cl] (9)
Over a period of 3 h, elemental iodine (106 mg, 0.42 mmol) was
added in small portions at 08C to a stirred solution of 1 (74 mg,
0.07 mmol). Stirring was continued and the reaction mixture was
warmed to room temperature overnight. Dichloromethane and io-
dobenzene were removed in vacuo (10À3 mmHg) to afford a yellow
solid. Recrystallization of the latter from CH2Cl2/hexane gave 59 mg
(62%) of pure 6 as yellow crystals, mp 1678C.
Tetraphenylphosphonium chloride (11 mg, 0.03 mmol) was added
to a solution of 4 (28 mg, 0.03 mmol) and the mixture was stirred
at room temperature overnight. The solvent was evaporated in va-
cuo to afford a white solid. Recrystallization of the latter from Et2O/
CH2Cl2 gave 33 mg (85%) of pure 9·1CH2Cl2 as colorless crystals of
mp 2288C.
2
1H NMR (CDCl3, 300.13 MHz, 294 K): d 3.57 [s, 1H, J(1HÀ117/119Sn)=
2
1H NMR (CDCl3, 400.25 MHz, 299 K): d 2.80 [s, 1H, J(1HÀ117/119Sn)=
66 Hz, J(1HÀ C)=129 Hz, CH], 7.39 (m, 9H, PhÀHm,p) 7.56 [m, 6H,
1
13
88 Hz, CH], 6.96–7.90 (complex pattern, 50H, Ph). 13C{1H} NMR
2J(1HÀ117/119Sn)=90 Hz, PhÀHo]. 13C{1H} NMR (CDCl3, 75.47 MHz,
(CDCl3, 75.47 MHz, 296 K): d: 117.3 [d, J(13CÀ P)=90 Hz, Ci (PPh4)],
1
31
294 K): d: 9.2 (CH), 129.0 [3J(13CÀ117Sn)=88 Hz, J(13CÀ119Sn)=89 Hz,
3
127.6 [3J(13CÀ117/119Sn)=73 Hz, Cm (SnPh)], 128.2 (Cp) (SnPh), 130.8
Cm], 131.4 [4J(13CÀ117/119Sn)=19 Hz), Cp], 135.1 [2J(13CÀ117/119Sn)=
66 Hz, Co], 136.3. No 1J(13CÀ117/119Sn) coupling constants were ob-
tained. 119Sn{1H} NMR (CDCl3, 111.92 MHz, 298 K): d À262 [2J(119SnÀ
117Sn)=311 Hz]. Anal. calcd for C19H16I6Sn3 (1361.8): C 16.8; H 1.2.
Found: C 17.0; H 1.2.
31
31
[d, 2J(13CÀ P)=12 Hz, Co (PPh4)], 134.4 [d, 3J(13CÀ P)=10 Hz, Cm
(PPh4)], 135.8 [d, 4J(13CÀ P)=3 Hz, Cp (PPh4)], 136.7 [2J(13CÀ
31
117/119Sn)=52 Hz, Co (SnPh)], 138.9 (Ci) (SnPh). The signal for the CH
carbon atom was not measured. 119Sn{1H} NMR (CDCl3, 149.26 MHz,
294 K):
d
À97. ESI–MS (negative mode): m/z 972.9
[(Ph2ClSn)3CH·Cl]À. Anal. calcd for C61H51Cl4PSn3 (1312.85): C 55.8; H
3.9. Found: C 55.4; H 4.1.
Synthesis of Tris(dichloridophenylstannyl)methane
HC(SnCl2Ph)3 (7)
Synthesis of (PPh4)2[(HC(SnCl2Ph)3·2Cl] (10)
To a solution of 6 (250 mg, 0.18 mmol) in CH2Cl2 (25 mL) was
added excess of silver chloride (260 mg, 1.81 mmol). The resulting
mixture was stirred at room temperature in the dark for 14 days.
The AgI that had formed and the non-reacted AgCl was removed
by filtration. The solvent of the filtrate was evaporated in vacuo
(10À3 mmHg) to afford a white solid. Recrystallization of the latter
from CH2Cl2/hexane gave 99 mg (66%) of pure 7 as colorless crys-
tals, mp 1768C.
Tetraphenylphosphonium chloride (41 mg, 0.11 mmol) was added
to a solution of 7 (44 mg, 0.05 mmol) in CH2Cl2 and the mixture
was stirred at room temperature overnight. The solvent was
evaporated in vacuo to afford a white solid. Recrystallization of the
latter from CH2Cl2/hexane gave 67 mg (85%) of pure 10 as color-
less crystals of mp 2528C.
1H NMR (CD2Cl2, 400.25 MHz, 299 K): d 4.35 [s, 1H, J(1HÀ117/119Sn)=
2
1H NMR (CDCl3, 400.25 MHz, 295 K): d 3.13 [s, 1H, 2J(1HÀ17119Sn)=
68/76 Hz, CH], 7.56 (m, 9H, PhÀHm, p) À7.79 [m, 6H, 2J(1HÀ
117/119Sn)=28 Hz, PhÀHo]. 13C{1H} NMR (CDCl3, 100.64 MHz, 297 K):
d: 33.2 (CH), 129.9 [3J(13CÀ117/119Sn)=100/105 Hz, Cm], 132.3 [4J(13CÀ
117/119Sn=21 Hz, Cp], 134.9 [2J(13CÀ117/119Sn)=68/73 Hz, Co], 137.8
104 Hz, CH], 7.06–8.18 (complex pattern, 55H, Ph). 13C{1H} NMR
1
31
(CD2Cl2, 75.47 MHz, 296 K): d 117.5 [d, J(13CÀ P)=90 Hz, Ci (PPh4)],
127.5 [3J(13CÀ117/119Sn)=88 Hz, Cm (SnPh)], 128.3 (Cp) (SnPh), 130.7
31
31
[d, 2J(13CÀ P)=13 Hz, Co (PPh4)], 134.5 [d, 3J(13CÀ P)=10 Hz, Cm
31
(PPh4)], 134.9 [Co (SnPh)], 135.7 [d, 4J(13CÀ P)=3 Hz, Cp (PPh4)],
1
(Ci). No J(13CÀ117/119Sn) coupling constants were obtained. 119Sn{1H}
153.5 (Ci) (SnPh). The signal for the CH carbon atom was not mea-
sured. 119Sn{1H} NMR (CD2Cl2, 149.26 MHz, 294 K): d À248. Anal.
calcd for C67H56Cl8P2Sn3 (1562.72): C 51.5; H 3.6. Found: C 51.1; H
3.9.
NMR (CDCl3, 149.26 MHz, 294 K): d À3 [2J(119SnÀ117/119Sn)=279 Hz].
Anal. calcd for C19H16Cl6Sn3 (813.09): C 28.1; H 2.0. Found: C 28.1; H
2.4.
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Synthesis of (11)
To a solution of 2 (300 mg, 0.25 mmol) in CH2Cl2 (20 mL) were
added 3 molar equivalents of silver perchlorate (155 mg,
0.75 mmol). The resulting mixture was stirred at room temperature
in the dark for 22 h. After the AgI that had formed had been re-
moved by filtration, the solvent of the filtrate was reduced in va-
cuo (10À3 mmHg) to a volume of approximately 2 mL. The addition
of iso-hexane (2 mL) caused precipitation of a small amount of 2 as
crystalline material that was separated by filtration. The solvent of
the filtrate was completely removed in vacuo, giving an amor-
phous white solid material. One part of the latter was dissolved in
CDCl3. An 119Sn NMR spectrum was recorded from this solution
(see below). Another part of the solid material was recrystallized
from CH3CN/hexane giving a few crystals of pure 11, mp 2298C.
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119Sn{1H} NMR (CDCl3, 149.26 MHz, 298 K): d À69 [2J(119SnÀ117Sn)=
237 Hz, integral 2.0, 2], À76 [2J(119SnÀ117/119Sn)=297/310 Hz,
13
2J(119SnÀ117Sn)=232 Hz, 1J(119SnÀ13 Ci)=592 Hz, 3J(119SnÀ Cm)=
2
13
69 Hz, J(119SnÀ Co)=52 Hz, integral 10.2], À83 [2J(119SnÀ117/119Sn)=
270/283 Hz, integral 1.0], À228 [2J(119SnÀ117/119Sn)=297/310 Hz, in-
tegral 5.7], À244 [2J(119SnÀ117/119Sn)=271/283 Hz, 2J(119SnÀ117Sn)=
370 Hz, integral 2.9]. IR(ATR): n=3394 (OH).
Acknowledgements
A.S.W. is grateful to the German Academic Exchange Board
(DAAD) for a scholarship.
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Keywords: anion complexation · organostannate complex ·
organotin oxocluster · tin · X-ray diffraction
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