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1187

X-ray diffraction and solid-state 119Sn CP-MAS

NMR studies of some triaryltin(IV) chlorides1
Jordan M. Geller, Ian S. Butler, Denis F.R. Gilson, Frederick G. Morin, Ivor Wharf,
and F. Bélanger-Gariépy

Abstract: The solid-state 119Sn cross-polarization (CP) magic angle spinning (MAS) NMR spectra of a series of
triaryltin chlorides of the form Ar3SnCl have been acquired. The indirect spin-spin coupling constants (J(119Sn-35Cl)),
quadrupolar-dipolar shifts (d(119Sn-35Cl)), and the 119Sn chemical shift tensors were extracted. For the spectrum of
triphenyltin chloride (I) the validity of the first-order perturbation approximation was tested by comparing results of
both the perturbation and cubic-equation approaches and a variable-temperature NMR study undertaken to investigate
the influence of the previously reported molecular motion in the solid. The X-ray crystal structures of the tris(o-
tolyl)tin chloride (II) and tris(p-tolyl)tin chloride (IV) complexes have been examined. They belong to the monoclinic
and triclinic space groups P21/n and P1, respectively, which are different from the previously reported tris(m-tolyl)tin
chloride (III) complex, which crystallizes in the space group R3 and has threefold molecular symmetry. The structures
and NMR properties of the complexes with meta-substituents are quite different from those with ortho- or para-
substituents having axially symmetric shift tensors with small spans and larger J values.
119
Key words: aryltin chlorides, magic angle spinning NMR, tin-chlorine spin-spin coupling, Sn chemical shift tensor,
crystal structure.
Résumé : On a déterminé les spectres RMN du 119Sn, à l’état solide et à la polarisation croisée (« CP ») de l’angle
magique de rotation (« MAS ») d’une série de chlorures de triarylétain de la forme Ar3SnCl. On en a extrait les cons-
tantes de couplage spin-spin indirectes, J(119Sn-35Cl), les déplacements quadripolaire-dipolaire, d(119Sn-35Cl), et les ten-
seurs du déplacement chimique du 119Sn. Pour le spectre du chlorure de triphénylétain (I), on a testé la validité de
l’approximation de la perturbation du premier ordre en comparant les résultats des approches de perturbation et
d’équation cubique avec les résultats d’une étude RMN à température variable réalisée dans le but d’étudier l’influence
du mouvement moléculaire rapportée antérieurement dans le solide. On a déterminé les structures par diffraction des
rayons X des chlorures de tris(o-tolyl)étain (II) et de tris(p-tolyl)étain (IV). Elles appartiennent respectivement aux
groupes d’espace monoclinique (P21/n) et triclinique (P1) qui diffèrent de celle rapportée antérieurement pour le
complexe du chlorure de tris(m-tolyl)étain (III) qui cristallise dans le groupe d’espace R3 et qui présente une symétrie
moléculaire ternaire. Les structures et les propriétés RMN des complexes portant un substituant en méta- sont très dif-
férentes de celles des produits portant des substituants en positions ortho- et para- qui possèdent des tenseurs de dépla-
cement axialement symétriques de faible portée et des valeurs de J plus élevées.

Mots clés : chlorures d’arylétain, RMN à l’angle magique de rotation, couplage spin-spin étain-chlore, tenseur de dé-
placement chimique du 119Sn, structure cristalline.
[Traduit par la Rédaction] Geller et al. 1195

Introduction of phenyl ring substituents on the biological and other prop-

Triaryltin compounds have been studied for many years
since the discovery of the biocidal properties of triphenyltin
hydroxide and acetate and their subsequent use as agricul-
tural fungicides (1). As part of an investigation of the effect
erties of triaryltin compounds, a wide range of o-, m-, and p-
substituted triaryltin hydroxides and acetates was synthe-
sized and tested for bioactivity (2, 3). This required the
preparation of the corresponding tetraaryltins and triaryltin
halides and the effect of varying the subsitituents on the aro-

Received 9 February 2003. Published on the NRC Research Press Web site at http://canjchem.nrc.ca on 1 October 2003.
Dedicated to Professor John Harrod in recognition of his contributions to Canadian chemistry.
J.M. Geller, I.S. Butler,2 D.F.R. Gilson,3 F.G. Morin, and I. Wharf. Department of Chemistry, McGill University, 801
Sherbrooke Street West, Montreal, QC H3A 2K6, Canada.
F. Bélanger-Gariépy. Départment de chimie, Université de Montréal, C.P. 6128, Succursale Centre-ville, Montréal, QC H3C 3J7,
Canada.
1
This article is part of a Special Issue dedicated to Professor John Harrod.
2
Corresponding author (e-mail: ian.butler@mcgill.ca).
3
Corresponding author (e-mail: denis.gilson@mcgill.ca).

Can. J. Chem. 81: 1187–1195 (2003) doi: 10.1139/V03-115 © 2003 NRC Canada

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1188
matic ring on their vibrational (Raman, IR) spectra (4, 5) has
been reported. In addition, 119mSn Mössbauer spectroscopic
studies of various para-substituted aryltin complexes have
also appeared (6, 7). More pertinent to this paper are two
solution-state 119Sn and 13C NMR studies (8, 9) of various
para-, meta- and ortho-substituted tetraaryltins (Ar4Sn) and
triaryltin halides (Ar3SnX; X = Cl, Br, I). For both the p-
and m-substituted Ar4Sn and Ar3SnX series, the 119Sn chem-
ical shifts could be correlated with various substituent pa-
rameters (σI, σR, σR0, σP, σP0) showing electronic effects due
to the ring substituents are sufficient to account for the ob-
served δ(119Sn) trends. We now report solid-state 119Sn stud-
ies of a wide range of triaryltin chlorides for comparison
with the earlier solution studies.
Solid-state NMR spectra often provide information that is
unavailable from solution spectra. Thus, when a probe nu-
cleus such as a 119Sn (I = 1/2) nucleus is bonded to a
quadrupolar nucleus, line splittings occur in the solid-state
NMR spectra, which can be analyzed to give information
about the electronic environment and bonding about the tin
nucleus. A review of the effects of quadrupolar nuclei on the
CP-MAS spinning spectra of spin 1/2 nuclei has been pub-
lished, which includes the tin-chlorine case (10), and the
31
P–35/37Cl case has also been reported (11). The spectra are
complicated by the presence of two isotopes: 35Cl (75%
abundant) and 37Cl (25% abundant). Both nuclei (I = 3/2)
have similar magnetogyric ratios (γ(35Cl) = 2.264 ×
107 rad s–1 T–1, γ(37Cl) = 2.184 × 107 rad s–1 T–1 (12)) and
nuclear quadrupole moments (Q(35Cl) = –8.165 × 10–30 m2
and Q(37Cl) = –6.435 × 10–30 m2 (13)).
Olivieri (14) developed a treatment of the splittings (∆νm)
in the MAS spectrum of a probe nucleus (I = 1/2) directly
bonded to a quadrupolar nucleus based on first-order pertur-
bation theory, which is valid in the limit χ/[4S(2S – 1)νs] << 1,
where νs is the Larmor frequency of the quadrupolar nucleus
and χ is the nuclear quadrupolar coupling constant. Thus,
with 35Cl and 37Cl, provided that χ/12νs << 1, the splittings
observed in the solid-state spectra under magic angle spin-
ning are given by eq. [1]:
[1] ∆νm = –msJIS + (3χD′/20νs)(3 cos2βD – 1 +
η sin2βD cos 2αD)[{S(S + 1)
– 3ms2}/{S(2S – 1)}]
where JIS is the spin-spin coupling constant, D′ = (D –
∆J/3), where D is the direct dipolar coupling constant (D =
(µo/4π)γ sγ Ih2/(4π2(rIS)3), and ∆J is the anisotropy in the spin-
spin coupling, while αD and βD are, respectively, the azi-
muthal and polar angles relating the internuclear vector to
the principal axis of the electric field gradient (EFG), and η
is the asymmetry in the field gradient. Equation [1] assumes
that the J tensor is colinear with the internuclear dipole vec-
tor. The second-order quadrupolar–dipolar splitting (d) is
given by 3χD′/20νs. In most Ar3SnCl compounds in the solid
state, the local symmetry about the Sn—Cl bond is approxi-
mately C3 (in some cases exactly so). Thus, it can be as-
sumed that the angle βD is 0° and with the value of αD
undefined because it is multiplied by sin2βD, eq. [1] is re-
duced to a simpler form
[2] ∆νm = –msJIS + (3χD′/10νs)[5/4 – ms2]
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Can. J. Chem. Vol. 81, 2003
with d now given by 3χD′/10νs.
The 119Sn-MAS NMR spectrum of triphenyltin chloride
was first reported in 1987 (15) followed soon after by the
application of the perturbation theory to describe the
multiplet from the (119Sn-35/37Cl) spin pair, but only an aver-
age value of |Jiso| over the two sites was extracted from the
spectra (16, 17). Values of the d and ∆J were reported (14,
18) but these values were based on an average d for the two
crystallographically nonequivalent tin sites (19), while a
more detailed analysis in terms of the two chlorine isotopes
was not attempted. NQR data have been reported for tri-
phenyltin chloride at 77 K (20) and at 303 K (21).
In the present study, the solid-state NMR spectrum of
triphenyltin chloride (I) has been fully re-examined with ex-
traction of J, d, and δ iso for both tin sites as well as consider-
ation of both (119Sn-35Cl) and (119Sn-37Cl) spin pairs. The
validity of the first-order perturbation approximation was
tested by comparing results of both the perturbation- (10,
14) and cubic-equation approaches (22), and a variable-
temperature NMR study undertaken to investigate the influ-
ence of the previously reported molecular motion in the
solid (23).
For comparison with (I) we also present the 119Sn CP-
MAS spectra of a series of triaryltin chloride complexes
with various substituents in the ortho-, meta-, and para-
positions (II – IX); see Table 4 for the numbering scheme.
To correlate the NMR parameters (J, d, D′) and chemical
shift tensor components (δ11, δ22, δ33) with molecular geome-
tries, full-crystal structures are needed. Although the struc-
tures of most of the Ar3SnCl complexes studied here have
been reported earlier (9, 24–26), in this paper we now add
the structures of (o-tolyl)3SnCl (II) and (p-tolyl)3SnCl (IV).
The solid-state NMR spectra of some triaryltin fluorides
have been reported (27) but these complexes differ from the
chlorides since, with the exception of tris(mesityl)tin fluo-
ride, they are five-coordinate and form polymeric chains in
the solid. The chlorides are all distorted tetrahedral mole-
cules with the shortest nonbonded distance between tin and
chlorine occurring in the tris(m-anisyl)tin chloride at 4.37 Å
(24), much longer than the sum of the van der Waals radii
(3.93 Å) (28).
Experimental
The triaryltin chlorides were either from previous prepara-
tions or synthesized by literature methods (8, 9). Solid-state
119
Sn NMR spectra were recorded at 111.7 MHz using a
Chemagnetics CMX-300 (7.05 T) spectrometer under condi-
tions of 119Sn-1H cross-polarization, high-power proton de-
coupling, and magic-angle spinning. The CP-MAS spectra
were obtained for approximately 250–300 mg of sample
packed into zirconia pencil-type rotors (7.5 mm diameter),
using pulse delays of 10–60 s, depending on the proton T1
value, and contact times of 2 or 3 ms. The number of tran-
sients ranged from 240–1992 depending upon the compound
in question. Line broadening of 0–10 Hz was applied and
the FIDs were zero filled to 8 K and 16 K points before
transformation. Different spinning rates, from 1600–
4000 Hz, were used to identify the centre band. Chemical
shifts are given with respect to external tetramethyltin
((CH3)4Sn) using the chemical shift of solid tetracyclohexyl-
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Geller et al. 1189

Table 1. Crystal structure data and structural refinements for two methyl-substituted complexes of the form
Ar3SnCl.
Aryl = o-Tolyl (II) p-Tolyl (IV)
Formula C21H21ClSn C21H21ClSn
MW (g mol–1) 427.518 427.518
Crystal color, habit Colourless, needle Colourless, block
Crystal size (mm) 0.70 × 0.09 × 0.05 0.62 × 0.57 × 0.53
Crystal system Monoclinic Triclinic
Space group P21/n P1
a (Å) 9.7918(1) 10.3481(6)
b (Å) 11.4896(1) 10.6811(7)
c (Å) 17.5620(1) 10.9412(9)
α (°) 90.00 70.971(7)
β(°) 100.1643(4) 65.190(6)
γ (°) 90.00 66.157(6)
V(Å3) 1944.78(3) 986.04(12)
Z 4 2
Dcalcd. (Mg m–3) 1.4601 1.4399
λ (Å) 1.54178 0.71073
µ (mm–1) 11.671 1.428
Diffractometer Bruker AXS SMART 2K Bruker P4
Scan type ω ω/2θ
Temperature (K) 293(2) 292(2)
Absorption correction Multiscana Gaussianb
Transmission range 0.27–0.65 0.92–0.94
Measured reflections 22 892 22 403
Unique reflections, Rint 3788, 0.0506 5601, 0.0215
Observed data, criterion 3228, I > 2σ(I) 5267, I > 2σ(I)
Θmax (°) 72.85 29.99
Refined parameters 212 212
Refinement on F2 F2
Range measured –11 ≤ h ≤ 12 –13 ≤ h ≤ 13
–13 ≤ k ≤ 11 –13 ≤ k ≤ 13
–21 ≤ l ≤ 21 –14 ≤ l ≤ 14
R1 (obs) 0.0328 0.0223
wR2 0.0872 0.0596
S 1.057 1.122
Extinction coefficient 0.00021(9) 0.0120(7)
Note: R1 = ∑(||Fo| – |Fc||)/∑|Fo|; wR2 = {∑[w(Fo2 – Fc2)2]/∑[w(Fo2)2]}1/2; w = 1/σ 2(Fo2). S = {∑[w(Fo2 – Fc2)2]/(n – p)}1/2
(n = number of data, p = number of refined parameters).
a
Reference 31.
b
Reference 32.

tin (–97.0 ppm) as an external secondary reference. The line
positions of the centre band and spinning sidebands were ex-
tracted using the program Peakfit (Jandel Scientific). Calcu-
lations of the shielding tensors were performed using the
method developed by Herzfeld and Berger (29) and the com-
putational program HBA version 1.4 (30).
X-ray crystallography
Both (II) and (IV) were recrystallized by dissolving in
ethanol, hot filtering through Celite, followed by slow evap-
oration over several days at room temperature. Crystal data
and structural refinement details are given in Table 1. For
both compounds (II) and (IV), data were processed by
XPREP (31) and the structures were solved by direct meth-
ods using SHELXS-97 (33) and refined using SHELXL-96
(34). Non-hydrogen atoms were refined with anisotropic
thermal parameters with H-atoms in calculated positions.
Scattering factors were from the usual source (35). Com-
pound (IV) was run with Mo Kα radiation since the crystals
were large and could not easily be cut.4

4
Data for (II) and (IV) may be purchased from the Directory of Unpublished Data, Document Delivery, CISTI, National Research Council
Canada, Ottawa, ON K1A 0S2, Canada (http://www/nrc.ca/cisti/irm/unpub_e.shtml for information on ordering electronically). CCDC
188728 and 188729 contain the crystallographic data for (II) and (IV). These data can be obtained, free of charge, via
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
U.K.; fax +44 1223 336033; or deposit@ccdc.cam.ac.uk).

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1190 Can. J. Chem. Vol. 81, 2003

Results and discussion Fig. 1. ORTEP diagram of tris(o-tolyl)tin chloride (XI) viewed
along the tin–chlorine bond with the chlorine atom in front
X-ray crystallography showing 30% thermal probability ellipsoids.
Tris(o-tolyl)tin chloride (II) and tris(p-tolyl)tin chloride
(IV) crystallize in monoclinic (P21/n) and triclinic (P1)
space groups, respectively. In both cases there is only one
molecule in the asymmetric unit and the geometry about tin
is distorted tetrahedral. ORTEP diagrams of (II) and (IV)
are shown in Figs. 1 and 2, respectively, and selected bond
lengths and angles are given in Table 2. In (II), the geometry
around tin closely resembles that found earlier for (o-
tolyl)3SnNCS (36) with two ortho-methyl groups (C-17 and
C-27) cis- to chlorine while the third (C-37) is trans, with
the phenyl ring close to coplanar with the Cl-Sn-C(31) plane
at a dihedral angle Cl-Sn-C(31)-C(36) of 19.9(3)°. For (o-
tolyl)3SnNCS, with two molecules in the asymmetric unit,
the corresponding angles are 10.1(3)° and 17.6(3)°. Com-
pound (IV) also has one phenyl ring nearly coplanar with
the Cl-Sn-C(31) plane, the dihedral angle Cl-Sn-C(31)-C(32)
being 17.9(2)°. Table 2 also includes data for tris(m-tolyl)tin
chloride (III), which belongs to the trigonal space group R3,
with the threefold rotation axis containing the Sn—Cl bond
(9). Two other meta-substituted complexes (tris(m-anisyl)tin
chloride (VI) (24) and tris(3,5-dimethylphenyl)tin chloride Fig. 2. ORTEP diagram of tris(p-tolyl)tin chloride (VII) viewed
(VIII) (9)) also crystallize in trigonal space groups and pos- along the tin–chlorine bond with the chlorine atom in front
sess axial molecular symmetry. In contrast, the ortho- showing 30% thermal probability ellipsoids.
substituted complexes tris(o-anisyl)tin chloride (V) (26) and
tris(mesityl)tin chloride(IX) (25) are monoclinic (P21/n).

119
Solid-state Sn CP MAS NMR spectra

Triphenyltin chloride
With two molecules in its asymmetric unit, the 119Sn
MAS centre band of (I) consists of two asymmetric overlap-
ping quartets, from the (119Sn-35Cl) and (119Sn-37Cl) spin
pairs, with intensities in the ratio of 3:1, for each of the tin
sites, for a total of 16 lines. Alarcón et al. (22) derived cubic
equations for both the spin-spin coupling and the
quadrupolar-dipolar splitting for I-S spin pairs, with S = 3/2,
which are valid when 1 < |χ/νs| < 3. As the |χ/νs| ratio be-
comes greater than 0.8, the observed splittings are smaller
than would be predicted by first-order theory. The nuclear
quadrupolar coupling constants (χ) have been reported as
33.50 and 33.97 MHz at 303 K (21). At 7.05 T the 35Cl and
37
Cl resonance frequencies (νs) are 29.39 and 24.47 MHz,
thus, the calculated |χ35/νs35| ratios are 1.16 and 1.14 and
|χ37/νs37| ratios are 1.10 and 1.08 for the two tin sites, respec-
tively. To consider the validity of using first-order perturba-
tion theory, the NMR parameters were extracted from the For comparison,the experimental and simulated spectra of
line positions in the 119Sn MAS spectrum of triphenyltin triphenyltin chloride are shown in Fig. 3. The simulated
chloride using both the first-order and the cubic-equation ap- spectrum is the sum of 16 lines broadened by Lorentzian
proaches and are given in Table 3. The differences are small, functions, eight from the coupling of 119Sn with 35Cl; the
with the largest deviations being in the spin-spin coupling line positions given by eq. [2] with the values for J(119Sn-
constant for one of the tin sites, which is underestimated by 35
Cl), d(119Sn-35Cl), and δiso(119Sn-35Cl) given in Table 3.
8 Hz or a 3% difference. From this comparison we assume The other eight lines are one-third of the intensity from cou-
that the underestimation of these couplings is small enough pling of 119Sn with 37Cl and their positions were calculated
to justify using the first-order perturbation equation to ana- assuming that the 119Sn isotropic shifts are the same and by
lyze the spectra of the complexes (II)–(XI), which also re- using the ratios J(119Sn-35Cl)/J(119Sn-37Cl) = γ(35Cl)/γ(37Cl)
quires that that their quadrupolar coupling constants are not and d(119Sn-35Cl)/d(119Sn-37Cl) = Q(35Cl)/Q(37Cl). The ex-
substantially different from that of triphenyltin chloride (I). perimental spectra represent the centre band with all side-

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Geller et al. 1191

Table 2. Selected bond lengths (Å) and angles (°) for the methyl-substituted complexes of the form
Ar3SnCl from X-ray diffraction.
o-Tolyl (II) m-Tolyl (III)a p-Tolyl (IV)
Bond Lengths (Å)
Sn—Cl 2.3760(10) 2.379(1) 2.3729(6)
Sn—C11 2.131(3) 2.124(2) 2.1207(18)
Sn—C21 2.135(3) — 2.1154(17)
Sn—C31 2.131(3) — 2.1171(18)
Bond Angles (°)
Cl-Sn-C11 104.11(9) 104.40(6) 104.25(5)
Cl-Sn-C21 105.99(10) — 104.03(5)
Cl-Sn-C31 102.03(12) — 104.82(5)
C11-Sn-C21 112.81(12) 114.03(14) 118.37(7)
C11-Sn-C31 116.27(13) — 110.83(7)
C21-Sn-C31 113.89(14) — 112.96(7)
Cl-Sn-C11-C12 –62.4(3) –23.7(1) –60.80(17)
Cl-Sn-C11-C16 118.8(2) 158.2(1) 113.50(16)
Cl-Sn-C21-C22 –49.4(3) — 100.06(17)
Cl-Sn-C21-C26 130.3(3) — –78.87(15)
Cl-Sn-C31-C32 157.7(3) — –17.89(17)
Cl-Sn-C31-C36 –19.9(3) — 165.17(16)
a
Reference 9.

Fig. 3. 119Sn CP-MAS centre band spectrum of triphenyltin chlo-
ride (I) at 7.05 T and room temperature; lower (experimental)
upper (calculated). The arrows indicate lines due to coupling to
37
Cl.
bands folded in, i.e., the spectrum that would be obtained at
infinite spinning speed.
Chemical shifts
Chemical shift data for all Ar3SnCl complexes are given
in Table 4. Solid-state 119Sn MAS spectra of compounds
(II)–(VIII) and (XI) show a single centre band consistent
with one molecule in the asymmetric unit as found in the
crystal structures of (II)–(VI) and (VIII). For (IX) and (X),
as with (I), more complex spectra are observed that corre-
spond to two isotropic shifts and thus, two chemically
inequivalent sites. The intensities of the resonances for the
two sites are equal, suggesting the presence of two different
molecules in the asymmetric unit, which is consistent with
the crystal structures of complexes (I) (19) and (IX) (25).
All isotropic solid-state 119Sn chemical shifts, except that
for (VIII), show a shift to higher frequency when compared
with the corresponding solution data but still follow the
same general trend. The differences, which range from 0.4
to 17 ppm, are moderate and reflect slight changes in geom-
etry about tin rather than a change in coordination on going
from solution to the solid state (37). The differences be-
tween solid and solution shifts (δsolid – δsolution) are smallest
for compounds containing meta-substituents, where the shifts’
differences range from +2.4 to +3.5 ppm in (III) and (VI),
while for (VIII) the difference is –2.3 ppm. Tris(mesityl)tin
chloride (XI) also has a small (δsolid – δsolution) difference but
for most other compounds with ortho- or para-substituents,
the (δsolid – δsolution) differences are larger, the largest being
17 ppm for tris(p-anisyl)tin chloride (VII). The exception is
(p-FC6H4)3SnCl for which the chemical shifts in solution
and solid states are effectively the same.
The orientations of the chemical shift tensor components
can by assigned by the known molecular symmetries of
these tin complexes. Thus, the meta-substituted compounds
(III), (VI), (VII) have axially symmetric chemical shift ten-

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1192 Can. J. Chem. Vol. 81, 2003

Table 3. NMR parameters for triphenyltin chloride (I) by perturbation and cubic-equation methods.
Perturbation theory Cubic equation
Parameter (eq. [1]) (ref. 22)
35
J Site 1, site 2 (Hz) 265(2), 258(1) 273(1), 267(1)
35
d Site 1, site 2 (Hz) –76(2), –68(4) –78(4), –71(2)
35
D′ Site1, site 2 (Hz) 440(10), 400(20) 450(20), 410(10)
∆J Site1, site 2 (Hz) –300(40), –180(70) –330(70), –230(40)
δiso Site 1 (ppm) –34.5 –34.4
δiso Site 2 (ppm) –32.3 –32.4
Note: Standard deviations in the average values in parentheses. For ∆J, the errors were propagated from the
standard deviations in D and d.

Table 4. Chemical shift parameters.

X3SnCl (X =) δiso Solution (ppm) δiso Solid (ppm) δ11 (ppm) δ22 (ppm) δ33 (ppm) Span (ppm)
Phenyl (I) –44.9 –34.5 0.292 –48a –72a 92a
–32.3
o-Tolyl (II) –32.3 –24.5 42 –22 –94 135
m-Tolyl (III)a –42.3 –38.9 –31 –31 –55 24
p-Tolyl (IV) –35.9 –23.9 50 –33 –88 138
o-Anisyl (V) –56.7 –42.7 37 –72 –93 129
m-Anisyl (VI) –44.0 –41.5 –31 –31 –62 31
p-Anisyl (VII) –27.4 –10.4 76 –41 –66 142
3,5-Xylyl (VIII) –39.7 –42.0 –27 –34 –65 38
–31b –31b –64b 33b
Mesityl (IX) –84.4 –82.6 –74a, b –74a, b –98a, b 24a, b
–82.0
p-Chloro (X) –39.3 –28.5 34a –47a –70a 104a
–26.8
p-Fluoro (XI) –39.6 –40.0 45 –62 –102 147
Note: Uncertainties: ±6 ppm on span, ±2 ppm on δ11, δ22, δ33.
a
Average of two Sn sites.
b
From the static spectrum.

sors with the more shielded component (δ// (δ33)) assigned to
the unique direction along the threefold rotation axis con-
taining the Sn—Cl bond, leaving δ⊥ (δ11, δ22) to the tri-
gonally symmetric plane perpendicular to the Sn-Cl axis.
The symmetry of the shift tensor is consistent with the axial
molecular symmetry found in the solid state. Systems with
ortho- or para-substituents have non-axially symmetric shift
tensors, hence the assignment of δ33 is less clear.
Tris(mesityl)tin chloride, although it has both ortho- and
para-substituents, has δ11 = δ22, suggesting a quasi-trigonal
molecular symmetry, which is consistent with the crystal
structure of (mesityl)3SnCl (25).
The 119Sn CP-MAS full NMR spectra of tris(o-anisyl)tin
chloride (V), tris(m-anisyl)tin chloride (VI), and tris(p-
anisyl)tin chloride (VII) complexes are shown in Fig. 4.
Similar spectra are also observed when the substituent is a
methyl group. Extensive sideband manifolds are seen for
(II), (IV), (V), (VII), (X), and (XI), indicating spans (δ11–
δ33) in the range of 129–147 ppm, consistent with these com-
pounds not being axially symmetric. In contrast, the spectra
of (III), (VI), and (VIII) have few sidebands due to their
much smaller spans (24–38 ppm). It is noteworthy that,
while there are large differences in the spans, the isotropic
chemical shifts show much smaller differences, particularly
for the ortho- and meta-anisyl complexes. This demonstrates
the utility of chemical shift tensor measurements in provid-
ing additional information unavailable from solution spectra.
For the archetype Ph3SnCl, the span of 92 ppm lies between
the two ranges given above.
Spin-spin coupling (J) and quadrupolar-dipolar
(d) constants
For complexes with a single chemical shift, there should
be two overlapping asymmetric quartets, with intensity ra-
tios of 3:1, arising from the 119Sn-35Cl and 119Sn-37Cl pairs,
respectively. In typical spectra, between three and five line
positions can be extracted, e.g., the spectrum of tris(m-
tolyl)tin chloride (Fig. 5). In cases where there are two iso-
tropic chemical shifts, these numbers are doubled. Experi-
mental and simulated spectra for complexes (V), (VI), and
(VII) are shown in Fig. 6; once again the experimental spec-
tra represent the centre band with all sidebands folded in.
Values of J(119Sn-35Cl) and d(119Sn-35Cl) are given in Ta-
ble 5. In general, the compounds with meta-substituents,
(III), (VI), and (VIII), have slightly larger coupling con-
stants, which range from 263 to 279 Hz, while compounds
with ortho- and para-substituents, (V)–(XI), range from 230
to 262 Hz. These values can be compared with the previ-
ously reported coupling constants for tribenzyltin chloride of
226 Hz and bis(acetylacetonato)tin chloride, of 276 Hz (17).

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Geller et al. 1193

Fig. 4. 119Sn CP-MAS spectra of the isomers of trianisyltin chlo-
ride at 7.05 T and 298 K: o-anisyl (V) 2000 Hz spinning speed
(top), p-anisyl (VIII) 2000 Hz spinning speed (middle), and m-
anisyl(III) 4000 Hz spinning speed (bottom).
Fig. 5. 119Sn CP-MAS centre band spectrum of tris(m-tolyl)tin
chloride at 7.05 T and 298 K. The spectrum contains one tin
chemical shift from which there are two overlapping quartets
shown in the top and second rows. The sum of the two quartets
gives the calculated spectrum (3rd row), which is similar to the
experimental spectrum (bottom).

Tris(mesityl)tin chloride (IX) exhibits the largest 1J(119Sn-

35
Cl) coupling constants, 332 and 328 Hz for the two sites.
Assuming that the Fermi contact mechanism is the dominant Fig. 6. 119Sn CP-MAS centre band spectra of the trianisyltin
contribution for tin-chlorine spin-spin coupling, then the s- chloride isomers at 7.05 T and 298 K. (a) o-Anisyl (V), (b) m-
character of the Sn—Cl bond in (IX) should be higher than anisyl (III), (c) p-anisyl (VIII) lower (experimental), upper (cal-
in the other Ar3SnCl complexes. Solution 1J(119Sn-13C) data culated).
for complexes (I)–(XI) have been reported (8, 9); these
range from 603 to 644 Hz except for (o-anisyl)3SnCl (V)
with a value of 685 Hz. However, the mesityl system (IX)
has a significantly smaller coupling of 596 Hz. A smaller
119
Sn-13C coupling is consistent with less s-character in the
Sn—C bonds and thus, more s-character in the Sn—Cl bond.
The quadrupolar-dipolar splittings (d(119Sn-35Cl)) range
from –72 to –83 Hz with no apparent trend. The signifi-
cantly smaller value of –21 Hz for (IX) may be the result of
a larger ∆J value, which would reduce the effective dipolar
splitting D′ and hence the value of d. A larger ∆J value is
consistent with the larger J observed and seems reasonable,
as it is unlikely that the nuclear quadrupole coupling con-
stant for this complex is four times smaller than those of the
other members of the series.
Calculation of the direct dipolar coupling constants (D)
requires the exact values of r(Sn-Cl), which are known for D′ be obtained from d = 3χD′/10νs. However, values of
all systems studied here except for (VII), (X), and (XI). χ(35Cl) and χ(37Cl) data are available only for (I) and only
With D′ = (D – ∆J /3), the determination of ∆J requires that in this case is a direct calculation of D′, and then ∆J, possi-

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1194 Can. J. Chem. Vol. 81, 2003

Table 5. Quadrupolar-dipolar coupling (d) and spin-spin coupling (J) constants.

35
R3SnCl (R =) J (Hz)a 35
d (Hz)a rSn-Cl 35Db
Phenyl (I) 262(4) –78(2) 2.3538(14)c –338(3)
254(1) –73(5) 2.3557(14) –337(3)
o-Tolyl (II) 230(2) –87(4) 2.3760(10) –328(2)
m-Tolyl (III) 263(9) –79(13) 2.379(1)d –327(2)
p-Tolyl (IV) 257(6) –81(12) 2.3729(6) –330(1)
o-Anisyl (V) 262(1) –79(2) 2.371(5)e –330(11)
m-Anisyl (VI)f 274 –83 2.3451(14)g –341
p-Anisyl (VII) 256(1) –82(6) NA NA
3,5-Xylyl (VIII) 275(2) –78(10) 2.3575(2)d –336(1)
Mesityl (IX)f 332 –21 2.3890(13)h –323(3)
328 –21 2.3890(14)h –323(3)
p-Chloro (X) 248(1) –75(3) NA NA
247(1) –72(5)
p-Fluoro (XI) 253(4) –81(8) NA NA
Note: Standard deviations in the average values obtained from the centre band and sidebands given in parentheses.
a
Determined from the (119Sn-35Cl) line positions.
b
Calculated from the Sn—Cl bond length (γ(119Sn) and γ(35Cl)).
c
Reference 19.
d
Reference 9.
e
Reference 26.
f
Centre band only.
g
Reference 24.
h
Reference 25.

ble. Harris and co-workers (38) have shown that the effec- Fig. 7. 119Sn CP-MAS centre band spectra of Ph3SnCl (I) at
tive dipolar coupling constant (D′) can be obtained from an 7.05 T and different temperatures.
analysis of the chemical shift anisotropy for each of the spin
states of the quadrupolar nucleus, but this method gave re-
sults with large errors, presumably because of incorrect in-
tensities resulting from the overlap of the (119Sn- 35Cl) and
(119Sn-37Cl) lines.

The effect of temperature on the spectrum of

triphenyltin chloride (I)
An earlier solid-state proton magnetic resonance second
moment study on (I) provided evidence for motion in the
solid state at about 300 K (23). This motion was considered
to be a C3 reorientation of the whole molecule along the
Sn—Cl bond axis. To investigate further the effect of this
motion on the spectrum of triphenyltin chloride, the solid-
state 119Sn CP-MAS spectra of (I) were obtained at three
temperatures (Fig. 7). The low-temperature spectrum at 248
K was taken to investigate the rigid phase, where no change
in the second moment of the proton resonance occurs; that at
room temperature represents the situation where motion has
just begun, while at high temperature (333 K) the second
moment transition is complete. The NMR parameters are
given in Table 6. The isotropic chemical shifts move to
lower frequency (more shielded) with increasing temperature
for both tin sites and the difference between the two tin sites
decreases with increased temperature, suggesting an averag-
ing of the two shifts at higher temperatures. After heating,
the room temperature spectrum was acquired again and was
identical to the unheated sample except that the line widths
had decreased. This suggests that an annealing process oc- stant is temperature dependent, however, this temperature
curs. The quadrupolar-dipolar splitting is expected to change dependence is a very small effect in comparison to the large
with temperature as the nuclear quadrupolar coupling con- changes in isotropic chemical shift.

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Geller et al. 1195

Table 6. NMR parameters for Ph3SnCl at various temperatures.

Parameter 248 K 295 K 333 K
119 35
J( Sn- Cl) Site 1, site 2 (Hz) 256(4), 261(4) 254(4), 262(4) 265(4), 266(4)
d(119Sn-35Cl) Site 1, site 2 (Hz) –79(4), –76(4) –73(2), –78(2) –86(4), –76(4)
δiso Site 1 (ppm) –33.99 –34.53 –34.94
δiso Site 2 (ppm) –31.01 –32.30 –33.22
δiso Average (ppm) –32.50 –33.41 –34.08
|δiso Site 1 – δiso site 2| 2.98 2.23 1.72
Span δ11–δ33a 82 92 80
δ11 (ppm)b 13 19 11
δ22 (ppm)b –43 –48 –45
δ33 (ppm)b –68 –72 –69
a
Average of the two sites ±6 ppm (systematic error).
b
Error is ±2 ppm.

Acknowledgements
This work was supported by grants from the Natural Sci-
ences and Engineering Research Council of Canada
(NSERC) and Fonds pour la formation de chercheurs et
l’aide à la recherche (Québec) (FCAR). We thank Dr. K.
Eichele and Dr. R.E. Wasylishen for the HBA version 1.4
program.
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