Intramolecularly coordinated organotin(IV) sulphides and their reactivity to iodine

Article abstract of DOI:10.1016/j.jorganchem.2007.05.025

Organotin(IV) sulphides (LSnPhS)₂ (3) and (LSnPh₂)₂S (4) containing O,C,O chelating ligand (L = 2,6-(t BuOCH₂)₂C₆H₃^-) were prepared by the reaction of parent organotin chlorides LSnPhCl₂ (1) and LSnPh₂Cl (2) with Na₂S · 9H₂O in toluene/water. Both sulphides were characterized by the help of elemental analysis, ESI-mass spectrometry, ¹H, ¹³C ¹¹⁹Sn NMR spectroscopy and the molecular structure of 3 was determined by X-ray diffraction techniques. Compounds 3 and 4 react with I₂ to organotin iodides LSnPhI₂ (5) and LSnPh₂I (6), instead of intended iodolysis of phenyl groups. Triorganotin iodide 6 reacts with the additional molecule of I₂ forming an ionic organotin compound [ LSnPh₂]⁺ I₃^- (7), which is unstable in solution and decomposes to Ph₂SnI₂ and 2,6-(tBuOCH₂)₂C₆H₃I (8).

Full text of DOI:10.1016/j.jorganchem.2007.05.025

Journal of Organometallic Chemistry 692 (2007) 3750–3757
www.elsevier.com/locate/jorganchem
Intramolecularly coordinated organotin(IV) sulphides and
their reactivity to iodine
a,
a
a
b
*
´
ˇ
˚ ˇ
´
Libor Dostal , Roman Jambor , Ales Ruzˇicka , Robert Jirasko ,
c
a
Jan Taraba , Jaroslav Holecˇek
a
ˇ
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, na´m. Cs. Legiı´ 565,
CZ – 532 10, Pardubice, Czech Republic
b
ˇ
Department of Analytical Chemistry, Faculty of Chemical Technology, University of Pardubice, na´m. Cs. Legiı´ 565,
CZ – 532 10, Pardubice, Czech Republic
Department of Inorganic Chemistry, Faculty of Science, Masaryk University of Brno, Kotla´rˇska´ 2, CZ – 611 37, Brno, Czech Republic
c
Received 19 February 2007; received in revised form 10 April 2007; accepted 15 May 2007
Available online 26 May 2007
Abstract
Organotin(IV) sulphides (LSnPhS)2 (3) and (LSnPh2)2S (4) containing O,C,O chelating ligand (L = 2,6-(t BuOCH2)2C6H3ꢀ) were pre-
pared by the reaction of parent organotin chlorides LSnPhCl2 (1) and LSnPh2Cl (2) with Na2S Æ 9H2O in toluene/water. Both sulphides
were characterized by the help of elemental analysis, ESI-mass spectrometry, 1H, 13C 119Sn NMR spectroscopy and the molecular struc-
ture of 3 was determined by X-ray diffraction techniques. Compounds 3 and 4 react with I2 to organotin iodides LSnPhI2 (5) and
LSnPh2I (6), instead of intended iodolysis of phenyl groups. Triorganotin iodide 6 reacts with the additional molecule of I2 forming
an ionic organotin compound [ LSnPh2]+ I3 (7), which is unstable in solution and decomposes to Ph2SnI2 and 2,6-(tBuOCH2)2C6H3I
ꢀ
(8).
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Tin; Sulphide; Chelating ligand; NMR spectroscopy; X-ray structure
1. Introduction
S, Se) [5]. Adamantane-like structures have been detected
in diorganotin sulphides in which two tin atoms are bridged
by a single methylene carbon atom [6] or propylene bridge
[7]. Recently, Dakternieks et al. also reported on anionic
diorganotin sulphides of the type [S(SnR2Cl)2Cl]ꢀ [8].
Monoorganotin sulphides can be usually encountered as
(RSn)4E6 compounds with adamantane-like structure [9].
On the other hand, triorganotin derivatives form simple sul-
phur bridged structures R3SnSSnR3 with various Sn–S–Sn
bond angles depending on groups R [10].
One of the possibilities of stable central Sn2S2 ring forma-
tion is using of chelating ligands [11]. The O,C,O – coordinat-
ing pincer-type ligand (2,6-[(EtO)2(O)P]2-4-tBuC6 H2ꢀ) was
used for stabilization of a rare example of organotin sulfide
containing terminal Sn–Cl bond 2,6-[(EtO)2(O)P]2-4-
tBuC2H6Sn(S)Cl [12]. Organotin sulphides were also used
as ligands in transition metals coordination sphere [13].
Organotin(IV) sulphides have been extensively studied
over the last two decades and a variety of interesting struc-
tures depending on the organic groups bonded to the cen-
tral tin atom both in the solid state and in solution have
been observed. The diorganotin compounds were shown
to form cyclic trimers (Me2SnS)3 and (Ph2SnS)3 [1] or a
polymer (iPr2SnS)n [2]. Dimeric structures with central
Sn2S2 core can be stabilized by bulky ligands (tBu2SnS)2
[3] or [(2,4,6-iPr3C6H2)2SnS]2 [4]. Tokitoh et al. reported
on utilization of sterically crowded aryls 2,4,6-triisopropyl-
phenyl (Tip) and 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl
(Tb) for formation of unusual (Tb)(Tip)SnE4 rings (E =
*
Corresponding author. Tel.: +420 466037163; fax: +420 466037068.
´
E-mail address: libor.dostal@upce.cz (L. Dostal).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.05.025

L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
3751
Here, we report on the reaction of intramolecularly coor-
dinated organotin chlorides LSnPhCl2 (1) and LSnPh2Cl
(2) containing another type of O,C,O – coordinaꢀting pin-
10 ml. Combined toluene fractions were dried over Na2SO4
and evaporated in vacuo to dryness. The crude product was
washed with hexane to yield 3: 0.5 g (63%). Mp: 224–226 ꢁC.
Anal. Calcd for C44H60Sn2O4S2 (MW 954.47): C, 55.37; H,
6.34; Found: C, 55.56; H, 6.54%. Positive-ion MS: m/z 995
[M+K]+; m/z 979 [M+Na]+, 100%; m/z 479 [LSnPhSH]+.
1H NMR (CDCl3): 1.03 and 1.05 (18H, s, (CH3)3CO),
4.75 and 4.85 (4H, s, OCH2), 7.23–7.37 (6H, m, Ar–
H3,4,5L and Ar–H3,4,5–Ph), 7.67 and 8.00 (2H, d, Ar–
H2,6–Ph). 13C NMR (CDCl3): 27.5 (s, (CH3)3CO), 65.3
and 65.5 (s, OCH2), 75.6 and 75.7 (s, (CH3)3CO), 126.4
and 126.6 (s, Ar–C3,5–L), 128.0 and 128.2 (s, Ar–C3,5–
Ph), 128.9 and 129.1 (s, Ar–C4-L), 129.2 overlap of two sig-
nals (s(br), Ar–C4–Ph), 135.9 and 136.1 (s, Ar–C2,6–Ph),
137.6 and 137.6 (s, Ar–C1-L), 147.4 and 147.5 (s, Ar–
C2,6–L), 148.4 and 148.5 (s, Ar–C1–Ph). 119Sn NMR
(CDCl3): ꢀ74.6 (2J(119Sn, 117Sn) = 226 Hz), ꢀ79.5
(2J(119Sn, 117Sn) = 226 Hz).
cer-type ligand
L
(L = 2,6-(tBuOCH2)2C6H3
)
with
Na2S Æ 9H2O yielding organotin sulphides (LSnPhS)2 (3)
and (LSnPh2)2S (4). Investigation on the reactions of the
resulting sulphides 3 and 4 with molecular iodine is also
included. All derivatives were characterized by elemental
1
analysis, ESI-MS, H, 13C and 119Sn NMR spectroscopy.
2. Experimental
2.1. General remarks
1H, 13C 119Sn NMR spectra were recorded on Bruker
AMX360 and Bruker500 Avance spectrometers respec-
tively, using 5 mm tuneable broad-band probes. ppropriate
chemical shifts in 1H, 13C and 119Sn NMR spectra were cal-
ibrated on the residual signals of the solvent (CDCl3:
d(1H) = 7.27 ppm and d(13C) = 77.23 ppm) or external
Me4Sn (d(119Sn) = 0.0 ppm). Positive-ion electrospray ioni-
zation (ESI) mass spectra were measured on an ion trap
analyzer Esquire 3000 (Bruker Daltonics, Bremen, Ger-
many) in the range m/z 50–1500. The samples were dis-
solved in acetonitrile and analyzed by direct infusion at
the flow rate 5 ll/min. The selected precursor ions were fur-
ther analyzed by MS/MS analyses under the following con-
ditions: the isolation width m/z = 8, the collision amplitude
in the range 0.8–1.0 V depending on the precursor ion sta-
bility, the ion source temperature 300 ꢁC, the tuning param-
eter compound stability 100%, the flow rate and the
pressure of nitrogen 4 l/min and 10 psi, respectively.
2.4. Synthesis of [2,6-(tBuOCH2)2C6H3SnPh2]2S (4)
Na2S Æ 9H2O (0.45 g, 1.9 mmol) in 30 ml of water was
added to a solution of 2,6-(tBuOCH2)2C6H3SnPh2Cl
(2.08 g, 3.73 mmol) in toluene (30 ml) and the reaction mix-
ture was stirred overnight. Then the toluene fraction was
separated and water layer was washed twice with toluene
10 ml. Combined toluene fractions were dried over Na2SO4
and evaporated in vacuo to dryness. The white material was
extracted with hexane (2 · 50 ml) and evaporating of the
solvent yielded 4: 1.1 g (54%). Mp: 128–131 ꢁC. Anal. Calcd
for C56H70Sn2O4S (MW 1076.62): C, 62.48; H, 6.55. Found:
C, 62.71; H, 6.62%. Positive-ion MS: m/z 1117 [M+K]+;
m/z 1101 [M+Na]+; m/z 523 [LSnPh2]+; m/z 467
[LSnPh2–butene]+; m/z 411 [LSnPh2-2*butene]+, 100%; m/
z 351 [LSnPh2-2*butene-2*HCOH]+. 1H NMR (CDCl3):
0.88 (18H, s, (CH3)3CO), 4.36 (4H, s, OCH2), 7.18–7.49
(13H, m, Ar–H). 13C NMR (CDCl3): 27.8 (s, (CH3)3CO),
66.6 (s, OCH2), 73.8 (s, (CH3)3CO), 126.6 (s, Ar–C3,5–L),
128.5 (s, Ar–C3,5–Ph), 128.9 (s, Ar–C4–Ph), 129.8 (s, Ar–
C4-L), 136.5 (s, Ar–C2,6–Ph), 143.4 (s, Ar–C1–Ph), 147.7
(s, Ar–C2,6–L), (Ar–C1-L) not detected. 119Sn NMR
(CDCl3): ꢀ84.4.
2.2. X-ray structure determination
The X-ray data for single crystals of 3, 5 and 6 were
obtained at 150 K using Oxford Cryostream low-tempera-
ture device on a Nonius KappaCCD diffractometer with
˚
Mo Ka radiation (k = 0.71073 A), a graphite monochro-
mator, and the / and x scan mode. The absorption correc-
tions were made [14] by integration or multi-scan [15]
methods. Data reductions were performed with DENZO-
SMN [16]. Structures were solved by direct methods
(Sir92) [17] and refined by full matrix least-square based
on F2 (SHELXL97) [18]. All hydrogen atoms were positioned
geometrically and refined on their parent carbon atoms,
2.5. Synthesis of 2,6-(tBuOCH2)2C6H3SnPhI2 (5)
I2 (115 mg, 0.46 mmol) was added to a solution of 3
(216 mg, 0.23 mmol) in CH2Cl2 (30 ml). The resulting mix-
ture was stirred for 12 h and then evaporated in vacuo. The
residue was extracted with hexane (2 · 50 ml) and evapora-
tion of the solvent gave 5 as pale yellow powder. Yield:
210 mg (66%). Mp: 122–125 ꢁC. Anal. Calcd for
C22H30SnO2I2 (MW 698.98): C, 37.80; H, 4.33. Found: C,
38.12; H, 4.56%. Positive-ion MS: m/z 573 [MꢀI]+; m/z
517 [MꢀIꢀbutene]+; m/z 461 [MꢀIꢀ2*butene]+, 100%.
˚
˚
with C–H = 0.93 A and Uiso(H) = 1.2 Ueq(C) H atoms,
and C–H = 0.96 A and Uiso(H) = 1.5 Ueq(C) for methyl
hydrogen atoms.
2.3. Synthesis of [2,6-(tBuOCH2)2C6H3SnPhS]2 (3)
Na2S Æ 9H2O (0.4 g, 1.7 mmol) in 30 ml of water was
added to a solution of 2,6-(tBuOCH2)2C6H3SnPhCl2
(0.85 g, 1.64 mmol) in toluene (30 ml) and the reaction mix-
ture was stirred overnight. Then the toluene fraction was
separated and water layer was washed twice with toluene
1
Negative-ion MS: m/z 127 [I]ꢀ, 100%. H NMR (CDCl3):
1.07 (18H, s, (CH3)3CO), 4.73 (4H, s, OCH2), 7.33 (2H, d,
Ar–H3,5–L), 7.41 (4H, m, Ar–H4-L and H3,4,5–Ph), 7.75

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L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
(2H, d, Ar–H2,6–Ph). 13C NMR (CDCl3): 27.8 (s,
(CH3)3CO), 64.9 (s, OCH2), 76.9 (s, (CH3)3CO), 127.2 (s,
Ar–C3,5–L), 128.6 (s, Ar–C3,5–Ph), 130.6 (s, Ar–C4-Ph),
130.8 (s, Ar–C4-L), 134.5 (s, Ar–C2, 6–Ph), 141.7 (s,
Ar–C1-Ph), 147.2 (s, Ar–C2,6–L), (Ar–C1-L) not detected.
119Sn NMR (CDCl3): ꢀ391.8.
(s, Ar–C3,5–L), 130.7 (s, Ar–C3,5–Ph), 132.6 (s, Ar–C4–
Ph), 134.8 (s, Ar–C4-L), 136.6 (s, Ar–C2,6–Ph), 140.2 (s,
Ar–C1–Ph), 143.9 (s, Ar–C2,6–L), (Ar–C1-L) not detected.
119Sn NMR (CDCl3): ꢀ20.7. Positive-ion MS: m/z 523
[LSnPh2]+, 100%; m/z 467 [LSnPh2–butene]+; m/z 411
[LSnPh2-2*butene]+. Negative-ion MS: m/z 381 [I3]ꢀ; m/z
127 [I]ꢀ, 100%.
2.6. Synthesis of 2,6-(tBuOCH2)2C6H3SnPh2I (6)
2.7.2. NMR data of the mixture of 2,6-(tBuOCH2)2C6H3I
(8) and Ph2SnI2 after complete decomposition of 7
I2 (31 mg, 0.12 mmol) was added to a solution of 4
(132 mg, 0.12 mmol) in CH2Cl2 (30 ml). The resulting mix-
ture was stirred for 12 h and then evaporated in vacuo. The
residue was extracted with hexane (2 · 50 ml) and evapora-
tion of the solvent gave 6 as pale yellow powder. Yield:
100 mg (63%). Mp: 130–133 ꢁC. Anal. Calcd for
C28H35SnO2I (MW 649.18): C, 51.81; H, 5.43 Found: C,
52.09; H, 5.65%. Positive-ion MS: m/z 523 [M ꢀ I]+,
100%; m/z 467 [MꢀIꢀbutene]+; m/z 411 [MꢀIꢀ2*butene]+.
1H NMR (CDCl3): 1.33 (18H, s, (CH3)3CO – 8), 4.47
(4H, s, OCH2 – 8), 7.44 (1H, t, Ar–H4 – 8) 7.47–7.52 (8H,
m, Ar–H3,5 – 8 and Ar–H3,4,5–Ph2SnI2), 7.67 (4H, d,
Ar–H2,6–Ph2SnI2). 13C NMR (CDCl3): 27.9 (s, (CH3)3CO
– 8), 69.2 (s, OCH2 – 8), 74.0 (s, (CH3)3CO – 8), 100.9 (s,
Ar–C1 – 8), 127.5 (s, Ar–C3,5 – 8), 130.7 (s, Ar–C3,5–
Ph2SnI2), 132.6 (s, Ar–C4–Ph2SnI2), 134.8 (s, Ar–C4 – 8),
136.6 (s, Ar–C2,6–Ph2SnI2), 140.2 (s, Ar–C1–Ph2SnI2),
143.9 (s, Ar–C2,6 – 8). 119Sn NMR (CDCl3): ꢀ242.2,
Ph2SnI2. Positive-ion MS: m/z 415 [8 + K]+; m/z 399
[8 + Na]+, 100%. Negative-ion MS: m/z 127 [I]ꢀ, 100%.
1
Negative-ion MS: m/z 127 [I]ꢀ, 100%. H NMR (CDCl3):
0.94 (18H, s, (CH3)3CO), 4.58 (4H, s, OCH2), 7.36–7.42
(9H, m, Ar–H3,4,5–L and Ar–H3,4,5–Ph), 7.77 (4H, d,
Ar–H2,6–Ph). 13C NMR (CDCl3): 27.9 (s, (CH3)3CO),
66.7 (s, OCH2), 75.4 (s, (CH3)3CO), 126.9 (s, Ar–C3,5–L),
128.7 (s, Ar–C3,5–Ph), 129.6 (s, Ar–C4–Ph), 130.3 (s, Ar–
C4-L), 136.0 (s, Ar–C2,6–Ph), 142.6 (s, Ar–C1–Ph), 147.9
(s, Ar–C2,6–L), (Ar–C1-L) not detected. 119Sn NMR
(CDCl3): ꢀ182.9.
3. Results and discussion
3.1. Organotin sulphides
The reaction of LSnPhCl2 (1) (L = 2,6-(tBuOCH2)2-
C6H3ꢀ) [19] with 1 equiv of Na2S Æ 9H2O in toluene/water
gives the expected diorganotin sulphide (LSnPhS)2 (3) in
good yield (Scheme 1A). The attempt to prepare
(LSnPhCl)2S by the reaction of 1 with Na2S Æ 9H2O in
1:0.5 ratio yielded only a mixture of 3 and starting 1 as
2.7. NMR tube experiment – reaction of 6 with I2 in 1:1
molar ratio
I2 (40 mg, 0.16 mmol) was put into a NMR tube under
argon atmosphere and then CDCl3 solution of 6 103 mg
(0.16 mmol) was added. The resulting solution was imme-
1
shown by H and 119Sn NMR spectroscopy (Scheme 1B).
The addition of the next 0.5 equiv of Na2S Æ 9H2O to this
mixture led to a smooth formation of 3.
1
diately studied by H, 13C and 119Sn NMR spectroscopy
and ESI mass spectrometry (see Section 3).
The dimeric nature (LSnPhS)2 of 3 was proven by ESI
mass spectra, where the molecular adduct with sodium
ion [M+Na]+ at m/z 979 as the base peak accompanied
by molecular adduct with potassium ion [M+K]+ at m/z
995 were detected. The 119Sn NMR spectra of 3 revealed
two signals of very similar chemical shifts at ꢀ74.6 and
ꢀ79.5 ppm and both are accompanied by satellites coming
from coupling with adjacent 117Sn tin nucleus 2J(119Sn,
2.7.1. NMR data for [2,6-(tBuOCH2)2C6H3SnPh2]+I3
(7)
1H NMR (CDCl3): 1.25 (18H, s, (CH3)3CO), 5.07 (4H, s,
OCH2), 7.40–7.69 (9H, m, Ar–H3,4,5–L and Ar–H3,4,5–
Ph), 7.82 (4H, d, Ar–H2,6–Ph). 13C NMR (CDCl3): 28.5
(s, (CH3)3CO), 65.5 (s, OCH2), 85.0 (s, (CH3)3CO), 124.9
ꢀ
Scheme 1. Preparation of compound 3.

L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
3753
1
117Sn) = 226 Hz. Analogously H and 13C NMR spectra
contained two sets of signals approximately in 1:1 integral
ratio in CDCl3 at room temperature. The presence of two
sets of signals in 1H, 13C and 119Sn NMR spectra of diorg-
anotin sulphides containing phenyl and chelating ligand
was attributed to the formation of two possible isomers –
cis/trans in respect to the central Sn2S2 ring [11b] and anal-
ogous isomers were also obtained also with simple aryl
ligands on the central tin atom [5a]. These findings prove
the presence of both cis and trans isomers in CDCl3 solu-
tion of 3 (Fig. 1).
ligand [2,6-[(EtO)2(O)P]2-4- tBuC2H6Sn(S)Cl]2 are a bit dif-
ferent (2.533 vs. 2.357 A) maybe as a consequence of stron-
˚
ger Sn–O intramolecular interactions in this compound
[12]. Similar non-symmetric Sn2S2 rings were also obtained
with other chelating ligands [11,20]. Both O,C,O chelating
ligands are placed mutually trans in respect to the central
Sn2S2 core in 3. The polyhedron of the central tin atom
can be described as a distorted bi-capped tetrahedron, since
both oxygen donor atoms are, although very weakly, coor-
dinated to the tin atom (O3–Sn1 2.927(7), O4–Sn1
˚
2.993(5) A) in cis position (O3–Sn1–O4 115.83(16)ꢁ). Both
The structure of one of these isomers trans-3 (single crys-
tals were obtained from solution containing both cis/trans
isomers) in the solid state was established by X-ray diffrac-
tion study (Fig. 2, Table 1). The molecular structure of
trans-3 is formed as a centrosymmetric dimer with planar
Sn2S2 core. The bond distances between the tin atoms and
sulphur atoms within this ring are nearly identical Sn1–S2
intramolecular Sn–O interactions in 3 are comparable to
those found in parent dichloride 1 (O–Sn 2.775(1) and
2.882(1) A) [19] but considerably weaker than values in
˚
organotin cations stabilized by the same O,C,O – coordinat-
ing pincer-type ligand (range of Sn–O distances 2.270(2)–
˚
2.394(3) A), where both oxygen donor atoms are coordi-
nated in trans fashion (range of O–Sn–O angles
148.90(6)–150.67(5)ꢁ) [21]. Similarly, stronger intramolecu-
lar Sn–O interactions were found in organotin compounds
containing another O,C,O – coordinating pincer-type
ligand (2,6-[(EtO)2(O)P]2-4-tBuC6H2ꢀ) [12,22].
˚
2.429(3) and Sn1–S2a 2.424(2) A as well as bonding angles
Sn1–S2–Sn1a 88.91(9)ꢁ and S2–Sn1–S2a 91.09(8)ꢁ. On the
other hand, Sn–S bond distances within central Sn2S2 ring
in organotinsulphide containing another O,C,O chelating
The reaction of LSnPh2Cl (2) [19] with 0.5 equiv of
Na2S Æ 9H2O in toluene/water gives desired triorganotin
sulphide (LSnPh2)2S (4) in moderate yield (Scheme 2). In
the positive-ion ESI mass spectra [M+Na]+ (m/z 1101)
and [M+K]+ (m/z 1117) adducts of molecule proved the
compostion of 4 (see Section 2). The 119Sn NMR spectrum
of 4 revealed signal at ꢀ84.4 ppm suggesting (pseudo)tetra-
hedral environment at the tin atom and is comparable to
that found for Ph3SnSSnPh3 (ꢀ54 ppm) [10b]. The 1H,
13C NMR spectra of 4 also contain only one set of signals
that is in accordance with non-existence of any other iso-
mer in solution of 4.
Fig. 1. Possible isomers cis(trans) of compound 3.
3.2. Reaction of organotin sulphides with I2
The attempt to form organotin iodide (LSnIS)2 by a
phenyl abstraction by the reaction of compound 3 and
two equivalents of I2 failed. Interestingly, elimination of
sulphur was observed and the product was characterized
as diorganotin compound LSnPhI2 (5) (Scheme 3). Similar
reaction was discovered by Wuest and co-workers, when
the reaction of hexaphenyldistannathiane with iodine affor-
ded Ph3SnI [23]. The value d(119Sn) = ꢀ391.8 ppm of 5 is
shifted upfield when compared to Ph2SnI2 ꢀ242.2 ppm
indicating the presence of an intramolecular Sn–O interac-
1
tion. However, the H and 13C NMR spectra of 5 contain
only one set of signals in the whole studied temperature
range (300–215 K) indicating fast dynamic dissociation-
association process of both ligands’ arms [24].
Fig. 2. ORTEP drawing (50% probability atomic displacement ellipsoids)
of trans-3. Hydrogen atoms have been omitted for clarity (symmetry code
Single crystals of 5 were obtained by crystallization from
saturated CHCl3/hexane solution (Table 1) and the molec-
ular structure of compound 5 is depicted in Fig. 3. Both
donor oxygen atoms in 5 are coordinated to the central
tin atom only very weakly with bond distances O1–Sn1
˚
a: ꢀx, ꢀy, ꢀz). Selected bond distance (A): S2–Sn1 2.429(3), S2a–Sn1
2.424(2), O3–Sn1 2.927(7), O4–Sn1 2.993(5), Sn1–C8 2.138(7), Sn1–C21
2.122(6). Selected bonding angles (ꢁ): S2–Sn1–S2a 91.09(8), Sn1–S2–Sn1a
88.91(9), O3–Sn1–O4 115.83(16), C8–Sn1–C21 114.8(3), C8–Sn1–S2a
113.2(2), C8–Sn1–S2 113.8(2), C21–Sn1–S2a 111.4(3), C21–Sn1–S2
110.3(2).
˚
2.843(3) and O2–Sn1 2.789(3) A, similarly to compound

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L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
Table 1
Crystal data and structure refinement of 3, 5 and 6
3
5
6
Empirical formula
Color
Crystal system
Space group
C44H60O4S2Sn2
Colourless
Monoclinic
P21/c
C22H30O2SnI2 Æ CHCl3
White
Monoclinic
P21/n
C28H35IO2Sn
Yellowish
Monoclinic
P21/cn
˚
a (A)
14.7660(8)
9.9300(10)
19.5960(14)
129.801(7)
2
16.749(3)
9.6214(19)
19.163(4)
110.73(3)
4
12.0610(13)
11.4860(6)
19.783(3)
98.638(10)
4
˚
b (A)
˚
C (A)
b (ꢁ)
Z
l (mmꢀ1
)
1.265
1.436
3.317
1.882
2.095
1.585
Dx (Mg mꢀ3
)
Crystal size (mm)
Crystal shape
0.3 · 0.2 · 0.15
Plate
0.2 · 0.07 · 0.05
Needle
0.43 · 0.31 · 0.25
Plate
h range (deg)
Tmin, Tmax
1–27.5
1–27.5
1–27.5
0.714, 0.815a
19892
0.654, 1.000b
18198
0.418, 0.623b
18061
No. of reflections measured
No. of unique reflections; Rint
No. of observed ref. [I > 2r(I)]
No. of parameters
Sc all data
Final Rc indices [I > 2r(I)]
wR2c indices (all data)
4978, 0.045
2899
236
1.173
0.056
0.141
1.064, ꢀ1.597
6028, 0.052
4880
286
1.065
0.038
0.098
1.414, ꢀ1.242
5891, 0.036
3440
289
1.293
0.058
0.165
1.213, ꢀ2.149
ꢀ3
˚
Dq, maximum, minimum, [e A
]
a
Correction by integration.
SORTAV program.
b
2
2 1=2
2
1=2
c
Definitions: R(F) = RiFojꢀiFcjj/R jFoj, wR2 ¼ ½RðwðF 2o ꢀ F 2c Þ Þ=RðwðF o2Þ ꢁ , S ¼ ½RðwðF o2 ꢀ F 2c Þ Þ=ðNreflns ꢀ NparamsÞꢁ
.
3. The coordination polyhedron of the tin atom in 5 can be
described as a bi-capped tetrahedron formed by C1, C17,
I1 and I2 atoms, that is cis attacked by two oxygen donor
atoms O1 and O2 (angle O1–Sn1–O2 120.17(9)ꢁ). The main
deviations from the ideal tetrahedral environment can be
seen in angles I1–Sn1–I2 88.81(3)ꢁ and C1–Sn1–C17
121.23(19)ꢁ as a consequence of present weak intramolecu-
lar Sn–O interactions.
Similarly, the treatment of triorganotin sulphide 4 with
1 equiv of I2 yielded organotin iodide LSnPh2I (6) instead
of phenyl abstraction (Scheme 3). Nevertheless, this reac-
tion provides an alternative path to compound 6, which
Scheme 2. Preparation of compound 4.
Fig. 3. ORTEP drawing (50% probability atomic displacement ellipsoids)
of 5. Hydrogen atoms have been omitted for clarity. Selected bond
˚
distance (A): O1–Sn1 2.843(3), O2–Sn1 2.789(3), Sn1–C1 2.137(4), Sn1–
C17 2.117(5), Sn1–I1 2.7664(7), Sn1–I2 2.7693(7). Selected bonding angles
(ꢁ): O1–Sn1–O2 120.17(9), C1–Sn1–C17 121.23(19), C1–Sn1–I1
115.01(11), C1–Sn1–I2 108.85(13), C17–Sn1–I1 107.36(15), C17–Sn1–I2
110.87(14), I1–Sn1–I2 88.81(3).
Scheme 3. Reactions of organotinsulphides 3 and 4 with I2.

L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
3755
was shown to be inaccessible by the iodolysis of LSnPh3
previously [21a]. Derivative 6 was characterized by ESI-
MS spectra, 1H and 13C NMR spectra. The value
d(119Sn) = ꢀ182.9 ppm of 6 is well comparable to the value
ꢀ204.7 ppm of the less sterically demanding analogue 2,6-
(MeOCH2)2C6H3SnPh2I [21a].
tional equiv of I2. So the treatment of 6 with I2 in a NMR
tube (CDCl3) led to a smooth (within 30 min) and ꢀclean
formation of ionic organotin derivative [LSnPh2]+I3 (7).
The presence of organotin cation was clearly established
by 1H NMR spectrum, where the signal of the CH2O group
is significantly shifted to lower field (5.07 ppm) and also
119Sn NMR spectrum revealed only one signal at
ꢀ20.7 ppm, which is a value typical for triorganotin cat-
ions containing O,C,O – coordinating pincer-type ligand
[21]. Compound 7 is then unstable in CDCl3 solution
and is slowly transformed to new products (d(1H,
CH2O) = 4.47 ppm and d(119Sn) = ꢀ242.2 ppm) (Fig. 5).
The plausible explanation is formation of organotin com-
pound Ph2SnI2 along with 2,6-(tBuOCH2)2C6H3I (8)
(Scheme 4).
There are several pieces of evidence for this statement: (i)
d(119Sn) = ꢀ242.2 ppm really corresponds to Ph2SnI2 [25]
(ii) there are no visible nJ(119Sn, 13C) couplings to aromatic
carbons of the ligand L in 13C NMR spectra, although
nJ(119Sn, 13C) are obtained for phenyls of Ph2SnI2
(2J(119Sn, 13C(2,6)) = 61.7, 3J(119Sn, 13C(3,5)) = 76.3,
4J(119Sn, 13C(4)) = 16.6 Hz) (iii) the signal which is appro-
priate to C-ipso of the ligand in compound 8 is significantly
shifted to higher field d(13C) = 100.9 ppm as a consequence
of the presence of the C–I bond, also other aromatic iodides
displayed d(13C) of C–I carbon close to this value (for exam-
ple, PhI 94.3 ppm, 2-(CH3)C6H4I 101.8 ppm, 2-
(CH2Cl)C6H4I 99.4 ppm, etc. [26]) (iv) the presence of 8
was unambiguously confirmed by ESI mass spectra of this
mixture, where signals at m/z 399 (m/z 415) correspond to
[8+Na]+ ([8+K]+) (v) finally 1H, 119Sn HMBC NMR spectra
revealed no cross-peaks between the tin signal at ꢀ242 ppm
and the region of OCH2 groups of ligand L in 1H NMR spec-
trum, but this cross peak was obtained in parent iodide 6.
This means that organotin cation incorporated in compound
7 undergoes an unusual attack of I3ꢀ, which leads to a dis-
ruption of a commonly very strong pincer ligand–metal
The molecular structure of 6 was determined by the help
of X-ray diffraction measurements (Fig. 4, Table 1). Only
one of the oxygen donor atoms O4 is coordinated to the
central tin atom through medium strong intramolecular
˚
interaction O4–Sn1 2.696(6) A (this value indicates stron-
ger intramolecular interaction, than that found in diorg-
anotin iodide 5). The second oxygen atom O3 interacts
˚
with the tin atom only insignificantly O3–Sn1 3.200(6) A.
The resulting coordination polyhedron of Sn1 can be
described as a distorted trigonal bipyramid with ligand
and phenyls ipso carbon atoms C5, C6 and C24 in the
equatorial plane (R of angles in SnC3 girdle 349ꢁ). The
axial positions are occupied by donor oxygen atom O4
and iodine I1 (O3–Sn1–I1 169.13(13)ꢁ). Similar coordina-
tion polyhedron has been recently found in triorganotin
carboxylate 2,6-(MeOCH2)2C6H3SnPh2(O2CCF3) [21a].
A crucial step of the preparation of 6 is to rigorously fol-
low 1:1 stoichiometric ratio of 4 and I2, otherwise product
1
6 is accompanied by an impurity detected by the H and
119Sn NMR spectroscopy (the signal at ꢀ242.2 ppm in
the 119Sn NMR and with d(1H, CH2O) = 4.47 ppm). The
explanation is that compound 6 is able to react with addi-
Fig. 4. ORTEP drawing (50% probability atomic displacement ellipsoids)
of 6. Hydrogen atoms have been omitted for clarity. Selected bond
˚
distance (A): O3–Sn1 3.200(6), O4–Sn1 2.696(6), Sn1–C5 2.143(4), Sn1–C6
2.152(8), Sn1–C24 2.119(8), Sn1–I1 2.7857(8). Selected bonding angles (ꢁ):
I1–Sn1–O4 169.13(13), C5–Sn1–C6 112.8(3), C6–Sn1–C24 119.4(3), C5–
Sn1–C24 116.3(3).
Fig. 5. 119Sn NMR spectra (CDCl3, 300 K) showing formation of 7 and
its decomposition to Ph2SnI2.

3756
L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
Scheme 4. Formation and decomposition of ionic compound 7.
(d) Y. Matsuhashi, N. Tokitoh, R. Okazaki, M. Goto, S. Nagase,
Organometallics 12 (1993) 1351;
(e) N. Tokitoh, M. Saito, R. Okazaki, J. Am. Chem. Soc. 115 (1993)
2065;
bond [27] and formation of Ph2SnI2. This reaction path rep-
resents novel chemical behaviour of the O,C,O – coordinat-
ing pincer-type ligand in organotin(IV) chemistry.
(f) M. Saito, N. Tokitoh, R. Okazaki, Organometallics 15 (1996)
4531.
4. Conclusions
[6] D. Dakternieks, K. Jurkschat, H. Wu, E.R.T. Tiekink, Organomet-
allics 12 (1993) 2788.
[7] D. Dakternieks, K. Jurkschat, D. Schollmeyer, H. Wu, J. Organomet.
Chem. 492 (1995) 145.
[8] J. Beckmann, D. Dakternieks, A. Duthie, C. Jones, K. Jurkschat,
E.R.T. Tiekink, J. Organomet. Chem. 636 (2001) 138.
[9] (a) K. Wraage, T. Pape, R. Herbst-Irmer, M. Noltemeyer, H.G.
Schmidt, H.W. Roesky, Eur. J. Inorg. Chem. (1999) 869;
(b) H. Berwe, A. Haas, Chem. Ber. 120 (1987) 1175;
(c) R.M. Harker, M.F. Mahon, K.C. Molloy, Main Group Met.
Chem. 19 (1996) 29;
To summarize, two novel organotin sulphides 3 and 4
were prepared and structurally characterized. Their reac-
tion with iodine proceeded to corresponding organotin iod-
ides 5 and 6 instead of the intended phenyl abstraction.
Moreover triorganotin compound 6 is able to react with
additional eq. I2 to give ionic triorganotin compound
[LSnPh2]+ I3 7 that is unstable in solution and decom-
ꢀ
poses to Ph2SnI2 and the organic compound 2,6-
(tBuOCH2)2C6H3I 8.
(d) C. Wagner, C. Raschke, K. Merzweiler, Appl. Organomet. Chem.
18 (2004) 147.
[10] (a) For example see: R.J. Batchelor, F.W.B. Einstein, C.H.W. Jones,
R.D. Sharma, Inorg. Chem. 27 (1988) 4636;
5. Supplementary material
(b) S. Kerschl, B. Wrackmeyer, D. Ma¨nnig, H. No¨th, R. Staudigl, Z.
Naturforschung 42b (1987) 387;
(c) C. Glidewell, D.C. Liles, J. Organomet. Chem. 224 (1981)
237.
CCDC 635831, 635687 and 635832 contain the supple-
mentary crystallographic data for 3, 5 and 6. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223 336 033; or e-mail:
deposit@ccdc.cam.ac.uk.
[11] (a) B.M. Schmidt, M. Dra¨ger, K. Jurkschat, J. Organomet. Chem.
410 (1991) 43;
(b) K. Jurkschat, S. van Dreumel, G. Dyson, D. Dakternieks, T.J.
Bastow, M.E. Smith, M. Dra¨ger, Polyhedron 11 (1992) 2747;
(c) O.S. Jung, J.H. Jeong, Y.S. Sohn, Polyhedron
2557;
8 (1989)
Acknowledgements
(d) A. Tzschach, K. Jurkschat, Pure Appl. Chem. 58 (1986) 639;
(e) D. Schollmeyer, J. Kalbitz, H. Hartung, A. Tzschach, K.
Jurkschat, Bull. Soc. Chim. Belg. 97 (1988) 1075.
The authors thank the Grant Agency of the Czech
Republic (Grant no. 203/07/0468) and the Ministry of
Education of the Czech Republic (VZ 0021627501) for
[12] M. Mehring, Ch. Lo¨w, M. Schurmann, F. Uhlig, K. Jurkschat, B.
¨
Mahieu, Organometallics 19 (2000) 4613.
[13] (a) M. Herberhold, U. Steffl, W. Milius, B. Wrackmeyer, Z. Anorg.
Allg. Chem. 624 (1998) 386;
´
financial support. R. Jirasko acknowledges the support of
grant project MSM0021627502 sponsored by The Ministry
of Education, Youth and Sports of the Czech Republic.
(b) L.F. Tang, J.F. Chai, Z.H. Wang, W.L. Jia, J.T. Wang,
Organometallics 21 (2002) 3675;
(c) L.F. Tang, J.F. Chai, S.B. Zhao, J.T. Wang, J. Organomet.
Chem. 669 (2003) 57.
References
[14] R.H. Blessing, J. Appl. Crystallogr. 30 (1997) 421.
[15] P. Coppens, in: F.R. Ahmed, S.R. Hall, C.P. Huber (Eds.),
Crystallographic Computing, Munksgaard, Copenhagen, 1970, pp.
255–270.
[16] Z. Otwinowski, W. Minor, Methods Enzymol. 276 (1997) 307.
[17] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J. Appl.
Crystallogr. 26 (1993) 343.
[1] (a) H.J. Jacobsen, B. Krebs, J. Organomet. Chem. 136 (1977) 333;
(b) B.M. Schmidt, M. Dra¨ger, J. Organomet. Chem. 399 (1990) 63.
[2] H. Puff, A. Bongartz, R. Sievers, R. Zimmer, Angew. Chem., Int. Ed.
17 (1978) 939.
[3] H. Puff, G. Bertram, B. Ebeling, M. Franken, R. Gattermayer, R.
Hundt, W. Schuh, R. Zimmer, J. Organomet. Chem. 379 (1989) 235.
[4] P. Brown, M.F. Mahon, K.C. Molloy, J. Chem. Soc., Chem.
Commun. (1989) 1621.
[18] G.M. Sheldrick, SHELXL-97, University of Go¨ttingen, Go¨ttingen,
1997.
´
˚
ˇ
´
ˇ
´
ˇ
[19] R. Jambor, L. Dostal, A. Ruzˇicka, I. Cısarova, J. Brus, J. Holecek,
[5] (a) Y. Matsuhashi, N. Tokitoh, R. Okazaki, Organometallics 12
(1993) 2573;
Organometallics 21 (2002) 3996.
[20] D. Dakternieks, R. Tozer, K. Jurkschat, E.R.T. Tiekink, Z. Kristal-
logr. 211 (1996) 857.
(b) N. Tokitoh, H. Suzuki, T. Matsumoto, Y. Matsuhashi, R.
Okazaki, M. Goto, J. Am. Chem. Soc. 113 (1991) 7047;
(c) N. Tokitoh, Y. Matsuhashi, R. Okazaki, Tetrahedron Lett. 32
(1991) 6151;
˚
´
´
[21] (a) B. Kasˇna´, R. Jambor, L. Dosta´l, A. Ruzˇicˇka, I. Cısarˇova, J.
Holecˇek, Organometallics 23 (2004) 5300;

L. Dosta´l et al. / Journal of Organometallic Chemistry 692 (2007) 3750–3757
3757
´
´
´
ˇ
´
ˇ
(b) B. Kasˇna, R. Jambor, L. Dostal, I. Cısarova, J. Holecek, B.
[23] M. Gallant, M. Kobayashi, S. Latour, J.D. Wuest, Organometallics
7 (1988) 736.
ˇ
´
Stıbr, Organometallics 25 (2006) 5139.
[22] (a) J. Fischer, M. Schurmann, M. Mehring, U. Zachwieja, K.
¨
[24] H. Handwerker, C. Leis, R. Probst, P. Bassinger, A. Grohmann, P.
Kiprof, F. Herdtweek, J. Blu¨mel, N. Auner, C. Zybill, Organomet-
allics 12 (1993) 2162.
Jurkschat, Organometallics 25 (2006) 2886;
(b) K. Peveling, M. Henn, Ch. Lo¨w, M. Mehring, M. Schurmann, B.
¨
´ˇ
´
´
Costisella, K. Jurkschat, Organometallics 23 (2004) 1501;
[25] J. Holecˇek, A. Lycˇka, K. Handlır, M. Nadvornık, Collect. Czech.
(c) M. Mehring, I. Vrasidas, D. Horn, M. Schurmann, K. Jurkschat,
¨
Organometallics 20 (2001) 4647;
(d) M. Mehring, M. Schurmann, K. Jurkschat, Organometallics 17
¨
Chem. Commun. 55 (1990) 1193.
[26] C.J. Pouchart, J. Behnke, Aldrich library of 13C and 1H FT-NMR,
Aldrich Chem. Company, Milwaukee, USA, 2005.
(1998) 1227.
[27] M. Albrecht, G. van Koten, Angew. Chem., Int. Ed. 40 (2001) 3750.