Organotin compounds containing a bulky (Me3Si)3C or related ligand. Crystal structures of {(Me3Si)3CMe(O2NO)Sn}2O, (PhMe2Si)3CSnMeCl2 and (PhMe2Si)3CSnCl3

Article abstract of DOI:10.1016/S0022-328X(98)00688-3

Some compounds having very bulky ligands, mainly (Me₃Si)₃C (denoted by Tsi) or (PhMe₂Si)₃C (denoted by Tpsi), attached to functional tin centres have been studied. Treatment of TsiSnR₂Cl, R=Me or Ph, with one equivalent of ICl gave the corresponding chloride TsiSnRCl₂, and use of an excess of ICl gave TsiSnCl₃ in both cases. Reaction of either chloride with one equivalent of Br₂ gave the dibromide TsiSnRBr₂; when an excess of Br₂ was used TsiSnMe₂Cl still gave the dibromide but TsiSiPh₂Cl gave the tribromide TsiSnBr₃. Reaction of TsiSnMe₂Br with AgSCN or Ag₂O gave TsiSnMe₂NCS and (TsiSnMe₂)₂O, respectively, but when the crude product from the reaction of TsiSnMeBr₂ with AgNO₃ was recrystallized from MeOH the nitrato-oxide {TsiMe(O₂NO)Sn}₂O was obtained. In a seemingly previously unreported type of reaction, the alkoxide TsiSnMe₂OEt reacted with ICl, Br₂, or I₂ to give TsiSnMe₂X, X=Cl, Br, or I, respectively, and Bu₃SnOEt likewise reacted with ICl to give Bu₃SnCl. The chlorides TsiSnMe₂Cl and TsiSnMeCl₂ gave the hydrides TsiSnMe₂H and TsiSnMeH₂ on treatment with LiAlH₄, but in the case of TpsiSnMe₂Cl the Tpsi-Sn bond was cleaved to give TpsiH. The compound (Me₃Si)₂C(SnMe₂Ph)(SiMe₂Cl) reacted with a 1 M proportion of AgBF₄ in CH₂Cl₂ with cleavage of the Sn-Ph bond to give the difluoride (Me₃Si)₂C(SnMe₂F)(SiMe₂F). The crystal structures of the monomeric compounds {TsiMe(O₂NO)Sn}₂O, TpsiSnMeCl₂ and TpsiSnCl₃ are reported; {TsiMe(O₂NO)Sn}₂O provides the first example of unidentate bonding of an NO₃ group to four-coordinate tin.

Full text of DOI:10.1016/S0022-328X(98)00688-3

Journal of Organometallic Chemistry 564 (1998) 215–226
Organotin compounds containing a bulky (Me3Si)3C or related ligand.
Crystal structures of {(Me3Si)3CMe(O2NO)Sn}2O,
(PhMe2Si)3CSnMeCl2 and (PhMe2Si)3CSnCl3
Salih S. Al-Juaid, Mustafa Al-Rawi, Colin Eaborn, Peter B. Hitchcock, J. David Smith *
School of Chemistry, Physics and En6ironmental Science, Uni6ersity of Sussex, Brighton BN1 9QJ, UK
Received 20 March 1998
Abstract
Some compounds having very bulky ligands, mainly (Me3Si)3C (denoted by Tsi) or (PhMe2Si)3C (denoted by Tpsi), attached
to functional tin centres have been studied. Treatment of TsiSnR2Cl, R=Me or Ph, with one equivalent of ICl gave the
corresponding chloride TsiSnRCl2, and use of an excess of ICl gave TsiSnCl3 in both cases. Reaction of either chloride with one
equivalent of Br2 gave the dibromide TsiSnRBr2; when an excess of Br2 was used TsiSnMe2Cl still gave the dibromide but
TsiSiPh2Cl gave the tribromide TsiSnBr3. Reaction of TsiSnMe2Br with AgSCN or Ag2O gave TsiSnMe2NCS and (TsiSnMe2)2O,
respectively, but when the crude product from the reaction of TsiSnMeBr2 with AgNO3 was recrystallized from MeOH the
nitrato–oxide {TsiMe(O2NO)Sn}2O was obtained. In a seemingly previously unreported type of reaction, the alkoxide Tsi-
SnMe2OEt reacted with ICl, Br2, or I2 to give TsiSnMe2X, X=Cl, Br, or I, respectively, and Bu3SnOEt likewise reacted with ICl
to give Bu3SnCl. The chlorides TsiSnMe2Cl and TsiSnMeCl2 gave the hydrides TsiSnMe2H and TsiSnMeH2 on treatment with
LiAlH4, but in the case of TpsiSnMe2Cl the TpsiꢀSn bond was cleaved to give TpsiH. The compound
(Me3Si)2C(SnMe2Ph)(SiMe2Cl) reacted with a 1 M proportion of AgBF4 in CH2Cl2 with cleavage of the SnꢀPh bond to give the
difluoride (Me3Si)2C(SnMe2F)(SiMe2F). The crystal structures of the monomeric compounds {TsiMe(O2NO)Sn}2O, TpsiSnMeCl2
and TpsiSnCl3 are reported; {TsiMe(O2NO)Sn}2O provides the first example of unidentate bonding of an NO3 group to
four-coordinate tin. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Crystal structure; Silicon; Tin; Trisyl; Tris(trimethylsilyl)methyl; Tris(dimethylphenylsilyl)methyl
1. Introduction
Tsi=(Me3Si)3C Tpsi=(PhMe2Si)3C
{TsiMe(O2NO)Sn}2O 1 TpsiSnMeCl2 2
TpsiSnCl3 3.
There have been many fruitful studies of compounds
in which the very bulky (Me3Si)C or a related ligand is
attached to a functional silicon centre but only a few,
and mainly rather limited, analogous studies of com-
pounds containing a functional tin centre [1–7]. In an
extension of earlier reports [5–7] we now describe the
preparation and reactions of some new tin derivatives,
mainly bearing the ligand (Me3Si)3C (denoted by Tsi)
or (PhMe2Si)3C (denoted by Tpsi), and present the
crystal structures of {TsiMe(O2NO)Sn}2O 1, TpsiSn-
MeCl2 2 and TpsiSnCl3 3.
2. Results and discussion
2.1. Preparation of organotin halides and their
reactions with ICl, Br2 or I2
The trichloride TpsiSnCl3 was obtained from TpsiLi
and SnCl4 but it was accompanied by a substantial
amount of TpsiCl. Treatment of TsiSnMe2Cl or Tsi-
SnPh2Cl with a 1 M proportion of ICl in CH2Cl2 for
* Corresponding author. Tel.: +44 1 273 678124; fax: +44 1 273
677196.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00688-3

216
S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
30 min at room temperature gave the corresponding
dichloride in good yield (Eq. (1)) and when an excess
of ICl was used the trichloride was obtained (Eq. (2)).
AgNO3 in acetone or when a solution of Ph2Sn(NO3)2
in CHCl3 was boiled with exposure to the air [8].
2.3. The alkoxides TpsiSnMe2OR (R=Me, Et)
TsiSnR2Cl+ICl (1 equiv.)
“TsiSnRCl2 (R=Me or Ph)
(1)
(2)
The ethoxide TpsiSnMe2OEt was unexpectedly ob-
tained, in high yield, when the product of the reaction
of TpsiLi with Me2SnCl2, presumably TpsiSnMe2Cl,
was recrystallized from boiling EtOH, the boiling last-
ing only 10 min. In contrast, reaction of TpsiSnMe2Cl
with MeOH under reflux was slow, 4 days being re-
quired for completion of the reaction. This large dif-
ference between the rates of reaction in MeOH and
EtOH is puzzling, since it seems much too large to be
attributed to the difference of ca. 13°C between the
boiling points of the solvents. There could have been
some LiOH present in the initial crude product as a
result of hydrolysis of residual TpsiLi during work-up,
but the amount of this (and hence of LiOEt formed
from it in EtOH) could not have been sufficient to use
up more than say 10% of the chloride.
TsiSnR2Cl+ICl (excess)“TsiSnCl3 (R=Me or Ph)
The analogous reaction of TsiSnMe2Cl or Tsi-
SnPh2Cl with a 1 M proportion of Br2 gave the dibro-
mide in each case (Eq. (3)); we suggest that the initial
reaction is to give the monobromide TsiSnR2Br and
BrCl and that the latter then cleaves an SnꢀR bond.
TsiSnR2Cl+Br2 (1 equiv.)
“TsiSnRBr2 (R=Me or Ph)
(3)
When an excess of Br2 was used, TsiSnMe2Cl still
gave only the dibromide, indicating that Br2 is less
reactive than ICl in cleavage of the SnꢀMe bond, but
TsiSnPh2Cl gave the tribromide TsiSnBr3, reflecting
the higher reactivity of the SnꢀPh bond towards
electrophiles.
No reaction occurred between TsiSnMe2Cl and I2 in
CCl4 for 18 h at room temperature or 4 h under
reflux, or between TsiSnPh2Cl and I2 in CH2Cl2 for 18
h at room temperature.
An interesting, and apparently novel, reaction was
observed when the ethoxide was treated with ICl in
CH2Cl2, the chloride being readily formed (Eq. (6)).
Corresponding reactions were found to take place with
Br2 and even I2 (Eq. (7)).
TpsiSnMe2OEt+ICl“TpsiSnMe2Cl (+EtOI?)
TpsiSnMe2OEt+X2
(6)
2.2. Reactions with sil6er salts
“TpsiSnMe2X (+EtOX?) (X=Br, I)
(7)
Treatment of TsiSnCl3 with an excess of AgBF4 in
CH2Cl2 gave the expected trifluoride TsiSnF3 in high
yield, and reaction of TpsiSnMe2Cl with AgNO3 gave
the expected nitrate TpsiSnMe2ONO2. The chloride
TpsiSnMe2Cl did not react with AgSCN in acetone
during 48 h at room temperature, but when the bro-
mide TpsiSnMe2Br was used formation of the isothio-
cyanate TsiSnMe2NCS was complete within 1 h (Eq.
(4)) [7]. Reaction of the bromide with Ag2O in CH2Cl2
for 24 h at room temperature gave the oxide in good
yield (Eq. (5)).
When an excess of ICl or Br2 was used an SnꢀMe
bond was cleaved, to give TpsiSnMeCl2 or TpsiSn-
MeBr2, respectively. However only the monoiodo com-
pound was obtained when a large excess of I2 was
used.
This type of reaction has not, as far as we can
ascertain, been observed previously for organotin
alkoxides. That it is probably general was confirmed
by formation of Bu3SnCl from Bu3SnOEt and ICl. It
could possibly find application for in situ generation
of (unstable) alkyl hypohalites ROX, which are useful
intermediates in organic synthesis [9].
TpsiSnMe2Br+AgSCN“TpsiSnMe2NCS
TpsiSnMe2Br+Ag2O“(TpsiSnMe2)2O
(4)
(5)
An unexpected outcome was observed when the
product of the reaction of the dibromide TsiSnMeBr2
with AgNO3 was, without isolation, recrystallized from
MeOH, the compound obtained, in 87% yield, being
the nitrato–oxide {Tsi(Me)(O2NO)Sn}2O, which was
identified by an X-ray diffraction study (see later).
Presumably this was obtained by hydrolysis of the
initially formed dinitrate TsiSnMe(ONO2)2 by water in
the MeOH, which was not dried before use. The ni-
trato–oxide {Ph2(O2NO)Sn}2O was shown some years
ago to be formed when Ph2SnI2 was treated with
2.4. Reactions of chlorides with LiAlH4
Reduction of the bromides TsiSnMe2Br and TsiSn-
MeBr2 with LiAlH4 was shown previously to give the
corresponding hydrides TsiSnMe2H and TsiSnMeH2
[1]. We found that the chlorides TsiSnRCl2 (R=Me,
Ph) behaved analogously to give the expected dihy-
drides in high yield (Eq. (8)), but TpsiSnMe2Cl gave
only the cleavage product TpsiH (Eq. (9)).
TsiSnRCl2+LiAlH4“TsiSnRH2 (R=Me, Ph)
(8)

S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
217
TpsiSnMe2Cl+LiAlH4“TpsiH (+Me2SnH2?)
2.5. The compounds (Me3Si )2C(SnPh3)2,
(Me3Si )2C(SnMe2Ph)2, (Me3Si )2C(SnMe2Ph)SiMe2Cl
and (Me3Si )2C(SnMe2F)SiMe2F
(9)
2.6. Crystal structures
2.6.1. {TsiMe(ONO2)Sn}2O, 1
The crystal of 1 was found to contain molecules of
C2 symmetry, disordered about the SnꢀOꢀSn linkage,
as shown in Fig. 1A, with site occupancies of 0.72 and
0.28. The disorder affects the accuracy of the geometri-
cal data, especially for the Tsi group. The molecular
structure of the major configuration is shown in Fig.
1B, and the selected bond lengths and angles shown in
Table 1 refer only to this configuration. The main
features are that: (a) the compound is monomeric (there
could in principle have been intermolecular
SnON(O)O…Sn coordination to give a polymer, as is
the case for corresponding Cl…Sn interaction in the
chloride–oxide (Me2ClSn)2O [12]); (b) the Tsi groups
are in a trans disposition with respect to the SnꢀOꢀSn
linkage; and (c) the NO3 ligand is bonded through only
one O atom.
An
attempt
to
obtain
the
compound
(Me3Si)2C(SnPh3)2 by treatment of (Me3Si)2CCl2 with
Ph3SnLi yielded (Me3Si)2CH(SnPh3) in 10% yield and
Ph3SnSnPh3 as the main product. However, the related
compound (Me3Si)2C(SnMe2Ph)2 was made by treat-
ment of (Me3Si)2C(SnMe2Cl)2 with phenyllithium. This
compound was used to provide a route (see Eqs. (10a)
and (10b)) to the chloride (Me3Si)2C(SnMe2Ph)SiMe2Cl
which was required in order to find out whether migra-
tion of the Ph group might accompany replacement of
the Cl atom by fluorine upon reaction with AgBF4.
(Migration of Me groups was previously observed in
the reactions of the iodide (Me3Si)2C(SnMe3)SiMe2I
with silver salts, including AgBF4 in CH2Cl2, which
gave exclusively the rearranged (Me3Si)3CSnMe2F [10].)
The compound (Me3Si)2C(SnMe2Ph)2 was treated with
one equivalent of MeLi in Et2O–THF to give
(Me3Si)2C(SnMe2Ph)Li. Addition of Me2SiCl2 to the
Crystal structures of tin(IV) nitrate and several
organotin nitrates have been reported [13]. In all but
one case the nitrato groups are bound in a bidentate
fashion, though sometimes very unsymmetrically; for
example, whereas in Sn(ONO2)4 the two SnꢀO bonds to
each NO3 group are identical within the experimental
solution
of
the
latter
then
gave
(Me3Si)2C(SnMe2Ph)SiMe2Cl in good yield.
(Me3Si)2C(SnMe2Ph)2+MeLi
“(Me3Si)2C(SnMe2Ph)Li
(10a)
(10b)
(Me3Si)2C(SnMe2Ph)Li+Me2SiCl2
“(Me3Si)2C(SnMe2Ph)(SiMe2Cl)
When the latter chloride was treated with a 1 M
proportion of AgBF4 in CH2Cl2 there was no reaction
for 24 h at room temperature, but when the mixture
was heated under reflux for 20 min reaction was com-
plete. However, the product, isolated in 96% yield, was
the difluoride (Me3Si)2C(SnMe2F)SiMe2F (Eq. (11)).
(Me3Si)2C(SnMe2Ph)(SiMe2Cl)+AgBF4
“(Me3Si)2C(SnMe2F)(SiMe2F)
(11)
It is noteworthy that each AgBF4 molecule supplies
two F atoms. Since SiꢀCl bonds are much less reactive
than SiꢀI bonds towards silver salts in compounds of
this general type, we assume that the initial reaction
involves attack at the SnꢀPh bond to give
(Me3Si)2C(SnMe2F)(SiMe2Cl) and (unstable) AgPh
with liberation of BF3, and that the latter then brings
about fluorination at Si. It is likely that the F atom in
(Me3Si)2C(SnMe2F)(SiMe2Cl) provides anchimeric as-
sistance to abstraction of Cl− by Ag+. (Compare such
assistance from F atoms in compounds of the type
(Me3Si)2C(SiMe2F)(SiMe2X) [11].)
Fig. 1. (A) Structure of {TsiMe(O2NO)Sn}2O, 1, showing the disor-
der about the SnꢀOꢀSn linkage. Occupancies: filled bonds 0.72, open
bonds, 0.28. (B) Structure showing the numbering scheme for the
major configuration.

218
S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
Table 1
˚
Selected bond lengths (A) and angles (°), with estimated standard
deviations in parentheses, for {(Me3Si)3CMe(O2NO)Sn}2O, 1
SnꢀO(1)
SnꢀC(1)
SiꢀC(1) mean
O(2)ꢀN
1.975(4)
2.120(11) SnꢀC(11)
1.928(10) SiꢀMe mean
1.25(2)
1.15(2)
SnꢀO(2)
2.109(10)
2.142(14)
1.923(12)
1.21(2)
O(3)ꢀN
O(4)ꢀN
O(1)ꢀSnꢀO(2)
O(1)ꢀSnꢀC(11)
O(2)ꢀSnꢀC(11)
93.1(4)
109.1(4)
111.3(5)
O(1)ꢀSnꢀC(1)
O(2)ꢀSnꢀC(1)
C(1)ꢀSnꢀC(11)
111.2(4)
104.5(4)
123.3(5)
C(1)ꢀSiꢀMe mean 111.1(6)
MeꢀSiꢀMe mean 107.7(9)
SiꢀC(1)ꢀSi mean
SnꢀO(2)ꢀN
O(2)ꢀNꢀO(4)
SnꢀC(1)ꢀSi(1)
SnꢀC(1)ꢀSi(3)
111.0(6)
125(1)
117(2)
111.6(5)
104.1(5)
SnꢀOꢀSn
127.5(5)
115(1)
128(2)
O(2)ꢀNꢀO(3)
O(2)ꢀNꢀO(4)
SnꢀC(1)ꢀSi(2)
Fig. 2. Molecular structure of TpsiSnMeCl2, 2.
108.0(5)
the site labelled Cl(2) being occupied by Cl and C
atoms in 64/36 ratio and the site labelled C(26) corre-
spondingly having Cl and C in 36/64 ratio. Selected
bond lengths and angles are shown in Table 2. The
uncertainty [14], in TpsiSnMe2ONO2 one O atom is
strongly bound at a distance of 2.095(5) A from Sn,
˚
and another interacts only weakly at a distance of
˚
SnꢀCl(1) bond length, 2.353(3) A, is slightly shorter
˚
˚
2.929(8) A (which is still 0.8 A below the sum of the
relevant van der Waals radii) [7]. The exception is
provided by the compound Me2Sn(OH)(ONO2), which
crystallizes as a dimer in which intramolecular OꢀSn
coordination makes the Sn atoms five-coordinate [15],
this possibly inhibiting bidentate coordination of the
NO3 group. Thus as far as we are aware 1 represents
the only example of monodentate coordination of this
group to a four-coordinate Sn centre.
˚
than that (2.380(3) A) in the monomeric
{(Me3Si)2CH}3SnCl [18], in which the Sn atom is four
coordinate and shows almost perfect tetrahedral ge-
ometry. The only other noteworthy feature is that the
bulk of the Tpsi group causes the Cl and Me ligands on
Sn
to
draw
together,
the
Cl(1)ꢀSnꢀCl(2),
C(26)ꢀSnꢀCl(1) and C(26)ꢀSnꢀCl(2) angles being
98.5(1), 103.6(2) and 107.2(2)°, respectively, with corre-
spondingly large C(1)ꢀSnꢀCl(1), C(1)ꢀSnꢀCl(2), and
C(1)ꢀSnꢀC(26) angles of 112.2(2), 113.7(2) and
119.3(3)°, respectively.
Relevant details of the structure of 1 are as follows.
˚
(a) The SnꢀO(2) bond length, 2.109(10) A, is the same
as that of the main OꢀSn bond in TpsiSnMe2ONO2. (b)
The SnꢀOꢀN angle, 125(1)°, is significantly larger than
the corresponding angle for the stronger OꢀSn bond in
The torsion angles about SiꢀC bonds show that the
three SiMe2Ph groups have the same configurations
˚
TpsiSnMe2ONO2, 116.6(4) A, confirming that in the
latter there is a definite secondary O…Sn interaction
that draws the N atom over towards the Sn. (c) There
is a planar geometry at the N atom, the sum of the
OꢀNꢀO angles being 360°. (d) The SnꢀOꢀSn angle,
127.5(5)°, is significantly smaller than that in
(Ph3Sn)2O, 137(3)°, in which the tin atoms are also
four-coordinate [16]. (e) There is substantial deviation
from ideal tetrahedral geometry at Sn, probably as a
consequence of the large size of the Tsi ligand; the
CꢀSnꢀO angles vary from 104 to 111°, the CꢀSnꢀC
angle, 123°, is wide, and the OꢀSnꢀO angle, 93°,
narrow.
Table 2
˚
Selected bond distances (A) and angles (°) in (PhMe2Si)3CSnMeCl2,
2, and (PhMe2Si)3CSnCl3, 3, with estimated standard deviations in
parentheses
2
3
SnꢀCl(1)
SnꢀCl(2)
SnꢀC(26)
SnꢀC(1)
SiꢀC(Ph) mean
SiꢀC(Me) mean
2.353(3)
2.312(4)
2.225(6)
2.173(7)
1.879(8)
1.879(9)
2.317(4)
2.16(2)
1.858(10)
1.854(12)
Cl(1)ꢀSnꢀCl(2)
C1ꢀSnꢀC(1) mean
Cl(1)ꢀSnꢀC(26)
Cl(2)ꢀSnꢀC(26)
C(1)ꢀSnꢀC(26)
C(1)ꢀSiꢀC mean
CꢀSiꢀC mean
98.5(1)
100.6(1)
117.3(1)
113.0(2)
103.6(2)
107.2(2)
119.3(3)
112.9(4)
105.8(4)
104.2(3)
114.2(4)
2.6.2. TpsiSnMeCl2, 2
This compound was shown to be monomeric in the
solid with the tin four-coordinate (see Fig. 2), unlike
the great majority of diorganotin dichlorides, which
form polymeric chains (though Ph2SnCl2 is probably
monomeric [17]). There was found to be disorder in-
volving one of the Cl groups and the Me group on Sn,
111.8(5)
107.0(5)
103.6(4)
114.7(4)
SnꢀC(1)ꢀSi mean
SiꢀC(1)ꢀSi mean

S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
219
3. Experimental
All reactions involving organo-lithium or -magne-
sium compounds were carried out under dry argon.
Solvents were carefullly dried by standard methods.
Solutions of MeLi in Et2O and BuLi in hexane were
purchased from Aldrich.
The IR spectra were recorded with a Perkin-Elmer
1720 FTIR Spectrometer. EI or, where indicated, FAB
mass spectra were obtained at 70 eV on a Kratos MS
80RF or MS25 spectrometer; m/z values refer to ions
containing 120Sn. The suggested ion assignments are not
intended to indicate fragmentation routes but they
provide further evidence that compounds containing
the Tpsi group give prominent ions at m/z 325, 309, 263
and 175 [5]. The NMR spectra were recorded with a
Fig. 3. Molecular structure of TpsiSnCl3, 3.
with respect to the substituents at the central carbon
atom, so that the C(SiMe2Ph)3 group has the propeller-
like symmetry found in TpsiH [19], TpsiBF2OH [20]
and [TpsiBH3]− [21]. (The Tpsi group in Tpsi-
SnMe2ONO2 has lower symmetry [7].) The largest
groups, Ph and SnMe2Cl, are staggered about the C−
Si bonds but the torsion angles are twisted from the
ideal 180° to 156–160° by repulsions between methyl
groups attached to adjacent silicon atoms in 1,3-posi-
tions. Such distortions have been observed in all Tpsi
derivatives studied so far.
1
Bru¨ker AC 250 spectrometer, for H at 250.13 MHz,
for 13C at 62.85 MHz, and for 29Si at 49.69 MHz
(reference SiMe4), for 19F at 75.42 MHz (reference
CFCl3), and for 119Sn at 93.3 MHz (reference SnMe4).
Coupling constants involving 117Sn and 119Sn are sepa-
rately indicated when satellites were clearly resolved;
otherwise only one value without the Sn mass mumber
is given.
2.6.3. TpsiSnCl3, 3
The starting materials TsiLi [23] and TpsiLi [24] were
prepared in situ by metallation of TsiH orTpsiH with
methyllithium in boiling THF. Metallation was 90–
98% within 1 h. A few drops of Me3SiOMe were added
to destroy any unchanged methyllithium before the
solution was used. The compounds TsiSiR2Cl, R=Me
or Ph, were made as described previously [5]. Several
compounds described here have been synthesised previ-
ously by other methods. Their identities were estab-
lished by C, H analysis and multinuclear NMR
spectroscopy. We have given details only when substan-
tial new information, e.g. about coupling constants, has
been obtained.
An X-ray diffraction study of this trihalide seemed
likely to be of interest since there appears to be no
previous report on the structure of a simple organotin
trihalide of the type RSnCl3. The structure was derived
from a set of strong sharp reflections and solved in a
centrosymmetrical trigonal space group with two inde-
pendent monomers in the asymmetric unit, one in a
general position and the other on the three-fold axis.
The molecules, each with C3 symmetry, are stacked in
chains with their principal axes parallel to c. Those in
one chain point in one direction, those in the second
chain point in the opposite direction, and those in the
third chain point randomly in either direction. If data
on additional broad reflections are included the struc-
ture can be indexed on the basis of a larger unit cell
with the same c axis. The data suggest that over limited
regions within the crystal the molecules in the third
chain are ordered and these regions give the weak
broad X-ray reflections. The strong sharp reflections
arise from the disordered regions. The molecular struc-
ture is shown in Fig. 3 and the bond lengths and angles
for the undisordered molecule are given in Table 2.
Those of the other molecule are not significantly differ-
ent. The values are very similar to those in TpsiSn-
MeCl2 and so are not discussed further. The
propeller-like configuration of the Tpsi group is
reflected in the trigonal symmetry of the lattice. The
compound TpsiSiCl3 has an almost identical structure
with similar lattice disorder. It is possible that it should
3.1. Reaction of (Me3Si )3CSnMe2Cl with ICl
A solution of ICl (2.5 mmol) in CCl4 was added
dropwise to a solution of (Me3Si)3CSnMe2Cl (1.0 g, 2.4
1
mmol) in CCl4. Monitoring by H NMR spectroscopy
showed that the reaction was complete within 30 min.
The solvent was then removed to leave a white solid,
which was recrystallised from hexane to give dichloro-
(methyl){tris(trimethylsilyl)methyl}stannane (1.0 g,
98%), m.p. 344 °C (lit. [1], 320°C). l(H) (CDCl3) 0.37
2
1
(27H, s, J(HSi) 6.4 Hz, J(HC) 118.6 Hz, SiMe3), 1.23
ppm (3H, s, 2J(H117Sn) 60 Hz, 2J(H119Sn) 62 Hz,
MeSn). l(C) (CDCl3) 4.6 (s, J(CSn) 26.8 Hz, J(CSi)
52.1 Hz, Me3Si), 12.6 (s, J(CSn) 455 Hz, MeSn) 19.9
3
1
1
(s, CSi3). l(Si) (CDCl3): 0.15. l(Sn) (CDCl3): 95.8, m/z:
(421 (35%, MꢀMe), 221 (100, MꢀMeꢀMe3SnCl), 201
(55, MꢀMeꢀMe2SnCl2), 73 (45 Me3Si), 59 (10, Me2HSi).
(
have been refined in P3 (See experimental section) not
P3 as reported [22].

220
S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
3.2. Reaction of (Me3Si )3CSnMe2Cl with an excess of
ICl
the solvent was removed to leave a white solid, which
was recrystallised from hexane to give dibro-
mo(methyl){tris(trimethylsilyl)methyl}stannane, (1.2 g,
95%), m.p. 290°C (dec.). The C, H analysis and 1H
NMR spectra were identical to those of
(Me3Si)3CSnMeBr2 described above.
A solution of ICl (6.0 mmol) in CCl4 (1.0 M) was
added dropwise to a solution of (Me3Si)3CSnMe2Cl (1.0
g, 2.4 mmol) in CCl4 (10 cm3) and the mixture was
stirred for 1 h. The solvent was removed to leave a
white solid, which was recrystallised from hexane to
give trichloro{tris(trimethylsilyl)methyl}stannane (1.0 g,
99%), m.p. 315°C (dec.), (lit. [1], 290°C, dec.). l(H)
3.6. Attempted reaction between I2 and
(Me3Si )3CSnMe2Cl
2
(CDCl3): 0.41 (s, J(HSi) 6.4 Hz, Me3Si); l(C) NMR
A 1 M solution of I2 in CCl4 (10 cm3) was added
dropwise with stirring to (Me3Si)3CSnMe2Cl (1.0 g, 2.4
mmol) in CCl4 (10 cm3) and the mixture was stirred
(CDCl3): 4.4 (s, 1J(CSi) 52.6 3J(CSn) 37.9 Hz, Me),
32.3 (s, 1J(CSn) 113 1J(CSi) 25.5 Hz, SnMe2). l(Si)
(CDCl3): 1.4. l(Sn) (CDCl3): –36.4 (s), m/z: 441 (20%,
MꢀMe), 221 (80, MꢀMeꢀMe2SnCl2), 201 (55,
MꢀMeꢀMeSnCl3), 73 (10, Me3Si), 59 (30, Me2HSi), 45
(15%, MeH2Si).
1
overnight. No change was detected by H NMR spec-
troscopy, and so the mixture was heated under reflux
for 4 h and then allowed to cool. Evaporation of the
solvent under reduced pressure gave unchanged
(Me3Si)3CSnMe2Cl (0.9 g, 90%), m.p. 337°C.
3.3. Reaction of (Me3Si )3CSnMe2Cl with Br2
3.7. Reaction of (Me3Si )3CSnMeCl2 with LiAIH4
A solution of Br2 (2.5 mmol) in CCl4 (2.5 cm3) was
added with stirring to a solution of (Me3Si)3CSnMe2Cl
(1.0 g, 2.4 mmol) in CCl4 (20 cm3). The reaction was
A solution of LiAlH4 (0.38 g, 10 mmol) in THF (10
cm3) was added dropwise with stirring under nitrogen
to a solution of (Me3Si)3CSnMeCl2 (2.0 g, 4.5 mmol) in
THF (20 cm3). The mixture was stirred for 5 min, the
solvent removed under vacuum, and the residue ex-
tracted with hexane. The hexane was evaporated from
the extract and the residue was recrystallised from
l
monitored by HMR spectroscopy and found to be
complete after 30 min. The solvent was removed to
leave a white solid which was recrystallised from hex-
ane and shown to be dibromo(methyl){tris(trime-
thylsilyl)methyl}stannane (1.1 g, 87%), m.p. 290°C
(dec.), (lit. [1], 318°C, dec.). l(Si) (CDCl3) 0.45 (s).
l(Sn) (CDCl3): +18.8, m/z 509 (20%, MꢀMe), 445 (33,
MꢀBr), 376 (20), 307 (18, MꢀMe2SiBrꢀHBr), 201 (30),
73 (70).
hexane to give
a
white solid identified as
methyl{tris(trimethylsilyl)methyl}stannane (1.5 g, 90%),
m.p. 211°C (dec.). IR w(SnH) (KBr) 1839 cm−1, l(H)
2
(CDCl3): l 0.22 (27H, s, J(HSi) 6.2 Hz, Me3Si), 0.31
(3H, s, MeSn), and 5.04 (q, 2H, 3J(HH) 2.4 Hz,
1
3.4. Reaction of (Me3Si )3CSnMeBr2 with AgNO3
1J(H119Sn) 1817 Hz, J(Hll7Sn) 1737 Hz, SnH2). l(C)
3
(C6D6): −8.45 (s, MeSn)), 4.22 (s, J(CSn) 18.6 Hz,
A solution of (Me3Si)3CSnMeBr2 (2.0 g, 3.8 mmol) in
CH2Cl2 (20 cm3) was added to a solution of AgNO3
(1.34 g, 7.8 mmol) in CH2Cl2 (20 cm3). The mixture was
stirred for 7 h with protection from light, then filtered
through charcoal. The solvent was removed under
reduced pressure to leave a white solid, which was re-
crystallised from MeOH to give bis{methyl(nitrato)
{tris(trimethylsilyl)methyl}tin) oxide (2.9 g, 87%), m.p.
Me3Si). l(Si) (C6D6): l 0.1 (s, Me3Si); l(Sn) (C6D6):
1
2
–206.8 (t of q, J (1l9SnH) 1817, J (SnH) 54.3Hz), m/z
(CI NH3): 353 (85%, MꢀMe), 217 (50), 187 (100,
MꢀMe3SnHꢀMe), 129 (40, Me2SiCHꢁSiMe2), 73 (90,
Me3Si).
When a sample of the product (0.10 g, 0.27 mmol)
was placed in an NMR tube and CH2Cl2 (2 cm3) was
1
added the H NMR spectrum was found to be identical
187–189°C. Anal. found: C, 31.1;
H
6.9.
with that of (Me3Si)3CSnMeCl2, and addition of an
authentic sample of the the latter only enhanced the
signals.
C22H60N2O7Si6Sn2. Calc.: 30.3; 6.9%. d(H)
C
H
(CDCl3): 0.27 (6H, s, MeSn), 0.34 (54H, s, Me3Si). l(C)
(CDCl3): 4.7 (Me3Si), 4.9 (MeSn). l(Si) (CDCl3): −
0.22. l(Sn) (CDCl3): 81.5, m/z 857 (10%, MꢀMe), 808
(10), 733 (30), 381 (80), 201 (70), 73 (100).
3.8. Reaction of (Me3Si )3CSnPh2Cl with ICl
A solution of ICl (1.9 mmol, 1.9 cm3) in CCl4 was
added dropwise to a solution of (Me3Si)3CSnPh2Cl (1.0
g, 1.8 mmol) in CCl4 (10 cm3) at room temperature and
the mixture was stirred for a further 3 h. The solvent
was then pumped away and the residue recrystallised
from hexane to give dichloro(phenyl){tris(trimethyl-
silyl)methyl}stannane (0.8 g, 88%), m.p. 162°C. Anal.
3.5. Reaction of (Me3Si )3CSnMe2Cl with an excess of
Br2
An excess of a 1 M solution of Br2 in CCl4 (10 mmol)
was added to (Me3Si)3CSnMe2Cl (1.00 g, 2.40 mmol) in
CCl4 (20 cm3). The mixture was stirred for 24 h then

S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
221
3.12. Reaction of (Me3Si )3CSnPh2Cl with I2
found: C, 38.0; H, 6.3. C16H32Cl2Si3Sn calc: C, 38.6; H,
6.4%. l(H) (CDCl3): 0.40 (27H, s, Me3Si), 7.4–7.8 (5H,
m, Ph). l(C) (CDCl3): 4.95 (3J(CSn) 27.6 Hz, Me3Si),
129.3 (C3) 129.9 (C4), 134.7 (C2), 143.4 (C1). l(Si)
A solution of I2 (20 mmol) in CCl4 (20 cm3) was
added to a solution of (Me3Si)3CSnPh2Cl [5] (1.0 g,
1.8 mmol) in CCl4 (10 cm3) and the mixture was
stirred overnight. The solvent was then removed to
leave a white solid which was shown by its analysis
1
(CDCl3), 0.4 (s, J(SiC) 53 Hz). l(Sn) (CDCl3): +10.2,
m/z 483 (100%, MꢀMe), 448 (60, MꢀHClꢀMe), 279
(30), 247 (35), 201 (35), 149 (40), 73 (50, Me3Si), 58 (25,
Me2Si), 45 (15, MeH2Si).
1
and H NMR spectrum to be unchanged starting ma-
terial, chloro(diphenyl){tris(trimethylsilyl)methyl}stan-
nane (0.90 g, 88%), m.p. 203 (Lit. [4] 208°C), with
NMR spectra which agreed with those obtained pre-
viously [5].
3.9. Reaction of (Me3Si )3CSnPh2Cl with an excess of
ICl
A solution of ICl (20 mmol) in CCl4 (20 cm3) was
added to a solution of (Me3Si)3CSnPh2Cl (1.0 g, 1.8
mmol) in CCl4 (10 cm3), and the mixture was stirred
overnight. The solvent was removed to leave a white
solid, which was recrystallised from hexane to give
white cube-like crystals of trichloro{tris(trimethyl)silyl)
methyl}stannane (0.8 g, 96%), m.p. 315°C (dec.) with
spectra identical with those given above for this com-
pound.
3.13. Reaction of (Me3Si )3CSnPhCl2 with LiAlH4
A solution of LiAlH4 (4.2 mmol) in THF (10 cm3)
was added to a solution of (Me3Si)3CSnPhCl2 (1.0 g,
2.0 mmol) in THF (10 cm3) under nitrogen. When the
addition was complete the solvent was removed, the
residue extracted with dry hexane, and the extract
filtered and evaporated to leave a white solid, which
was
recrystallised
from
hexane
to
give
3.10. Reaction of (Me3Si )3CSnPh2Cl with Br2
phenyl{tris(trimethylsilyl)methyl}stannane, (0.81 g,
94%), m.p. 138°C (dec.). IR (Nujol) w(SnꢀH) 1840
cm−1. (Because of difficulties in combusting the com-
pound a satisfactory analysis could not be obtained.)
A solution of Br2 (2.0 mmol) in CCl4 (2.0 cm3) was
added dropwise to a solution of (Me3Si)3CSnPh2Cl (1.0
g, 1.8 mmol) in CCl4 (10 cm3) and the mixture stirred
for 1 h. The solvent was then removed and the white
solid recrystallised from hexane to give dibro-
mo(phenyl){tris(trimethylsilyl)methyl}stannane, (0.9 g,
85%), m.p. 241°C.
2
l(H) (C6H6): 0.25 (27H, s, J(1HSi) 6.2 Hz, Me3Si), 5.9
1
1
(2H, s, J(H119Sn) 1865 Hz, J(H117Sn) 1782 Hz, SnH2)
7.05–7.83 (m, 5H, Ph). l(C) (C6H6): 4.4 (Me3Si), 128.8,
129.2, 138.5 (Ph). l(Si) (C6H6) 0.36. l(Sn) (C6H6)
−193. m/z 415 (30, MꢀMe), 337 (25, MꢀMeꢀPhH), 247
(30), 217 (100), 187 (55), 129 (40), 73 (60). When a
sample was dissolved in CH2Cl2 in an NMR tube the
1H NMR spectrum was found to be identical with that
of (Me3Si)3CSnPhCl2, and addition of an authentic
sample of the latter only enhanced the signals.
Anal. found: C, 32.8; H, 5.3. C16H32Br2Si3Sn. Calc:
C, 32.8; H, 5.5%. l(H) (CDCl3): 0.40 (27H, s, Me3Si),
3
7.45–7.85 (5H, m, Ph). l(C) (CDCl3): 5.0 (s, J(CSn)
27.3 Hz, Me3Si), 129.0 (C3), 130.6 (C2), 134.8
(C4), 143.3 (C1). l(Si) (CDCl3): 0.7. l(Sn) (CDCl3):
−38.3. m/z 571 (25%, MꢀMe), 507 (70, MꢀBr),
492(60), 427(70), 327(30), 307(70), 201(50), 136(80), 73
(100).
3.14. Preparation of (Me3Si )3CSnF3
3.11. Reaction of (Me3Si )3CSnPh2Cl with an excess of
Br2
A solution of (Me3Si)3CSnCl3 (2.0 g, 4.4 mmol) in
CH2Cl2 (20 cm3) was added dropwise during 10 min to
a solution of AgBF4 (1.0 g, 5.1 mmol) in CH2Cl2 (10
cm3). The mixture was stirred for 3 h with protection
from light then filtered. The solvent was removed from
the filtrate to leave a white solid which was recrys-
tallised from hexane to give trifluoro{tris(trimethyl-
silyl)methyl}stannane (1.7 g, 94%), m.p. 211°C (dec.).
Found: C, 29.4; H, 6.9. C10H27F3Si3Sn. Calc.: C, 29.6;
H, 6.6%. l(H) (C6D6) 0.26. l(C) (C6D6): 4.4 (3J(CSn)
37.5 Hz, Me3Si). l(Si) (C6D6) 1.0. l(Sn) (C6D6): −33.0
l(F) (C6D6) −145.1 (J(FSn) 3458 Hz). m/z 393 (10%,
MꢀMe), 217 (30), 201 (50), 165 (90), 129 (15), 85 (30),
73 (100).
A solution of Br2 (10.0 mmol) in CCl4 (10.0 cm3) was
added dropwise to a solution of (Me3Si)3CSnPh2Cl (1.0
g, 1.8 mmol) in CCl4 (20 cm3). The mixture was stirred
for 6 h and the solvent then removed to leave a white
solid, which was recrystallised from hexane to give
tribromo{tris(trimethylsilyl)methyl}stannane, (0.9 g,
91%), m.p. 290°C (dec.). l(C) (CDCl3) 4.6 (1J(CSi)
3
52.6, J(CSn) 38.4 Hz, Me3Si). l(Si) (CDCl3): 1.7 (s).
l(Sn) (CDCl3) −236 ppm. m/z 573 (40%, MꢀMe), 509
(48, MꢀBr), 265 (60, MꢀMeꢀMe2SnBr2), 201 (85,
MꢀMeꢀMeSnBr3), 136(95), 73 (100), 43 (90).

222
S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
In an attempt to displace a further Me group from
tin the experiment was repeated but with the mixture
heated under reflux. A complex mixture of products
was obtained and not further investigated.
3.15. Preparation of (Me2PhSi )3CSnMe2OEt
A solution of Me2SnCl2 (9.5 g, 43 mmol) in 1:1
THF/Et2O (20 cm3) was added dropwise to a solution
of (Me2PhSi)3CLi (43 mmol) in THF (30 cm3) during
10 min at room temperature. The mixture was heated
under reflux for 10 min and the solvent then removed.
The pale yellow residue was extracted into CH2Cl2 (50
cm3), the extract was filtered, and the solvent was
removed. The residue was dissolved in boiling EtOH
and the solution was allowed to cool to room tempera-
ture to give white crystals of ethoxy(dimet-
hyl){tris(dimethylphenylsilyl)methyl}stannane, (20 g,
76%), m.p 130°C. Anal. found: C, 56.2: H, 7.1.
C29H44OSi3Sn. Calc.: C, 56.9; H, 7.2%. l(H) (CD2Cl2)
0.57 (18H, s, Me2Si), 0.59 (6H, s, Me2Sn), 1.24 (t,
CH3CH2O), 3.81 (q, CH2O), 6.97–7.3 (15H, m, Ph).
l(C) (CD2Cl2): 4.8 (Me2Si), 4.9 (Me2Sn), 21.0
(CH3CH2O), 60.5 (CH2O), 129.0 (C4), 127.7 (C3), 136.2
(C2), 141(Cl). l(Si) (CD2Cl2): −5.94. l(Sn) (CD2Cl2)
92.7. m/z 597 (20%, MꢀMe), 551 (40, MꢀEtOHꢀMe),
402 (20, MꢀMe3SnOEt), 309 (40) 250 (20), 197 (35), 165
(25), 135 (100), 73 (30).
3.18. Reaction of (Me2PhSi )3CSnMe2OEt with Br2 in
2/1 molar ratio
A solution of Br2 (1.63 mmol) in CCl4 was added
dropwise to a solution of (Me2PhSi)3CSnMe2OEt (2.0
g, 3.2 mmol) in CCl4 (10 cm3) and the mixture was
stirred for 1 h. The solvent was then pumped off to
leave a white solid, which was recrystallised from hex-
ane (10 cm3) to give bromo(dimethyl){tris(dimethyl-
phenylsilyl)methyl}stannane (1.9 g, 91%), m.p. 186°C.
Anal. found: C, 50.2; H, 6.2. C27H39BrSi3Sn. Calc.: C,
50.15; H, 6.0%. l(H) (CDCl3): 0.70 (18H, s, Me2Si),
2
0.96 (6H, s, J(HSn) 56 Hz, Me2Sn), 6.81–7.3 (15H, m,
1
3
Ph). l(C) (CDCl3): 4.7, J(CSi) 52.9, J(CSn) 14 Hz)
Me2Si), 8.5, (1J(CSn) 363 Hz, Me2Sn), 127.6 (C3), 129.0
(C4), 135.7 (C2), 139.5 (1J(CSi) 33.4 Hz, C1). l(Si)
(CDCl3): −5.7. l(Sn) (CDCl3): 82. m/z 631 (12%,
MꢀMe), 551 (40, MꢀMeꢀHBr), 402 (30 MꢀMe3SnBr),
340 (5, MꢀMe2PhSnBr), 309 (60), 197 (10), 175 (15),
135 (100), 73 (20).
3.16. Reaction of (Me2PhSi )3CSnMe2OEt with ICl
A solution of ICl (3.3 mmol) in CCl4 was added
dropwise to a solution of (Me2PhSi)3CSnMe2OEt (2.0
g, 3.2 mmol) in CCl4 (10 cm3), and the mixture was
stirred for 1 h. The solvent was then removed to leave
a white solid, which was recrystallised from hexane (10
cm3) to give chloro(dimethyl){tris(dimethylphenyl-
silyl)methyl}stannane. (1.9 g, 96%), m.p. 188°C. (Lit.
3.19. Reaction of (Me2PhSi )3CSnMe2OEt with an
excess of Br2
A solution of Br2 (10.0 mmol) in CCl4 (10.0 cm3) was
added to a solution of (Me2PhSi)3CSnMe2OEt (2.0 g,
3.2 mmol) in CCl4 (10 cm3). The mixture was stirred for
3 h and the reaction monitored by 1H NMR spec-
troscopy. The solvent was then removed to leave a
white solid, which was recrystallised from hexane (10
cm3) to yield dibromo(methyl){tris(dimethylphenyl-
silyl)methyl}stannane (2 g, 87%), m.p. 211°C. Anal.
found: C, 43.2; H, 5.0. C26H36Br2Si3Sn. Calc.: C, 43.8;
H, 5.0%. l(H) (CDCl3): 0.83 (18H, s, Me2Si), 1.55 (3H,
s, 2J(HSn) 56.7 Hz, MeSn), 6.8–7.37 (15H, m, Ph).
1
[5] 186°C). l(Si) −5.7. The C, H analysis and H, 13C
and 119Sn NMR spectra were identical with those re-
ported previously [5].
3.17. Reaction of (Me2PhSi )3CSnMe2OEt with an
excess of ICl
1
l(C) (CDCl3): 4.7 (3J(CSn) 16.3 Hz, J(CSi) 53.2 Hz,
A solution of ICl (10 mmol) in CCl4 was added to a
solution of (Me2PhSi)3CSnMe2OEt (2.0 g, 3.3 mmol) in
CCl4 (10 cm3), and the mixture was stirred for 3 h. The
solvent was then removed to leave a white solid, which
was recrystallised from hexane to give dichloro(me-
thyl){tris(dimethylphenylsilyl)methyl}stannane (1.9 g,
95%), m.p. 182°C. l(H) (CDCl3): 0.76 (18H, s, Me2Si),
Me2Si), 17.0 (J(CSn) 425 Hz, Me2Sn), 127.8 (C3), 129.4
(C4), 135.9 (C2), 138.3 (1J(CSn) 50 Hz, C1). l(Si)
(CDCl3): −5.4. l(Sn) (CDCl3): −7.5. m/z 710 (10%,
M), 695 (10, MꢀMe), 633 (10, MꢀPh), 615 (90,
MꢀMeꢀHBr), 537 (50, MꢀBrꢀMeBr), 402 (40,
MꢀMeꢀMe2SnBr2), 309 (75), 197 (70, PhSn), 135 (100,
Me2PhSi), 73 (85, Me3Si), 43 (97, MeSi).
2
1.18 (3H, s, J(HSn) 63.4 Hz, MeSn), 6.89–7.36 (15H,
m, Ph). l(C) (CDCl3): 4.6 (Me2Si), 15.0 (MeSn), 127.7
(C3), 129.4 (C4), 135.8 (C2), 138.1 (C1). l(Si) (CDCl3):
−5.5. l(Sn) (CDCl3): 75.7. m/z 622 (5%, M), 607 (5,
3.20. Reaction of (Me2PhSi )3CSnMe2OEt with an
excess of I2
MꢀMe),
571
(10,
MꢀHClꢀMe),
452
(10,
MꢀMe2PhSiCl), 437 (5, MꢀMe2PhSiClꢀMe), 309, 237
(10), 197 (20), 175 (40), 135 (100), 73 (50), 43 (30).
A solution of I2 (10.0 mmol) in CCl4 (10 cm3) was
added to a solution of (Me2PhSi)3CSnMe2OEt (0.90 g,

S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
223
1.46 mmol) in CCl4 (10 cm3) and the mixture was
stirred for 3 h. The solvent was removed to leave a
white solid, which was recrystallised from hexane (10
cm3) to give iododimethyl{tris(dimethylphenylsilyl}
methyl}stannane (0.92 g, 90%), m.p. 187°C. Anal.
found; C, 46.8; H, 5.9. C27H39ISi3Sn. Calc.: C, 46.6; H,
5.6%. l(H) (CDCl3) 0.73 (s, 18H, Me2Si), 1.2 (s, 6H,
2J(HSn) 51 Hz, Me2Sn), 6.70–7.4 (m, 15H, Ph). l(C)
(CDCl3): 4.8 (Me2Si), 9.25 (1J(CSn) 351 Hz, Me2Sn,),
127.5 (C3), 128.9 (C4), 135.7 (C2), 139 7 (Cl). l(Si)
(CDCl3): −5.7. l(Sn) (CDCl3): −8.9. m/z 679 (3,
MꢀMe), 567 (40, MꢀI), 551 (20, MꢀMeꢀHI), 489 (25,
(1H, s, CH), 7.1–7.3 (15H, m, Ph) (see ref. [19] for
shifts in CCl4). l(C) (C6D6): 1.77 (s, J(CSi) 53.5 Hz,
Me2Si), 0.45 (s, CH), 128.4 (C3), 128.7 (C4), 133.6 (C2),
142.1 (C1). l(Si) (C6D6): −4 3.
1
3.24. Reaction of (Me2PhSi )3CSnMe2Cl with MeOH
A solution of (Me2PhSi)3CSnMe2Cl (2.0 g, 3.3 mmol)
in MeOH (20 cm3) was heated under reflux. The pro-
gress of the reaction was monitored by 1H NMR
spectroscopy and after 4 days the solvent was removed
to give methoxydimethyl{tris(dimethylphenylsilyl)met-
hyl}stannane, (Me2PhSi)3CSnMe2OMe, (1.9 g, 96%),
m.p. 132°C. Anal. found: C, 56.1; H, 7.2.
C28H42OSi3Sn. Calc.: C, 56.3; H, 7.0%. l(H) (CDCl3)
MꢀPhꢀHI),
402
(50,
MꢀMe3SnI),
340
15,
MꢀMe2PhSnI), 325 (80), 309 (90), 263 (25), 247 (45),
197 (50), 175 (47), 135 (100), 78 (95), 43 (100).
3
3.21. (Me2PhSi )3CSnMe2ONO2 and
(Me2PhSi )3CSnMe2NCS
0.63 (18H, s, Me2Si), 0.66 (6H, s, Me2Sn), 3.7 (3H, s, J
(HSn) 41 Hz, OMe), 7.0–7.37 (15H, m, Ph). l(C)
(CDCl3) 4.5 (Me2Si), 4.7 (Me2Sn), 52.8 (OMe), 127.3
(C3), 128.6 (C4), 135.6 (C2), 140.2 (C1). l(Si) (CDCl3):
−5.9. l(Sn) (CDCl3): 92.6. m/z 583 (25%, MꢀMe), 551
(40, MꢀMeꢀMeOH), 521 (10, MꢀPh), 505 (10,
MꢀPhꢀMeH), 489 (5, MꢀPhꢀMeOH), 403 (12,
MꢀMeꢀMe4Sn), 341 (30, MꢀPhꢀMe4Sn), 309 (45), 279
(30, MꢀPhꢀMe3PhSn), 227 (20, Me2PhSn), 197 (30,
PhSn), 175 (25), 151 (35, Me3PhSi), 135 (100, Me2PhSi),
73 (40, Me3Si), 43 (25, MeSi).
The preparations of these compounds were described
previously [7].
3.22. Reaction of (Me2PhSi )3CSnMe2Br with Ag2O
A solution of (Me2PhSi)3CSnMe2Br (2.0 g, 3.0 mmol)
in CH2Cl2 (15 cm3) was added to a suspension of Ag2O
(1.00 g, 4.3 mmol) in CH2Cl2 (10 cm3) and the mixture
was stirred in an open vessel for 24 h. The solvent was
then removed to leave a white solid, which was recrys-
tallised from hexane (10 cm3) and found to be bis[-
dimethyl{tris(dimethylphenylsilyl)methyl}]tin oxide (1.6
g, 92%), m.p. 222°C. Anal. found: C, 56.6; H, 6.9.
C54H78OSi6Sn2. Calc.: C, 56.3; H, 6.8%. l(H) (CDCl3):
0.69 (36H, s, Me2Si), 0.82 (12H, s, Me2Sn), 6.6–7.3
(30H, m, Ph). l(C) (CDCl3): 4.7 (1J(CSi) 53 Hz,
3.25. Reaction of (Me2PhSi )3CLi with SnCl4 in THF
A solution of (Me2PhSi)3CLi (12.0 mmol) in THF
(30 cm3) was added dropwise with stirring during 20
min to a suspension of SnCl4 (3.1 g, 12.0 mmol) in
THF (25 cm3) at 0°C. The mixture was stirred for 1 h
at room temperature, the solvent then removed, and the
residue extracted with CH2Cl2 (30 cm3). The solvent
was evaporated from the extract and the residue recrys-
tallised from hexane (50 cm3) to give trichloro
{tris(dimethylphenylsilyl)methyl}stannane (2.0 g, 25%),
m.p. 222°C. Anal. found: C, 46.5; H, 5.3%.
C25H33Cl3Si3Sn. Calc.: C, 46.7; H, 5.1%. l(H) (CDCl3):
1
3J(CSn) 15 Hz, Me2Si), 5.2 (1J(C117Sn) 388, J(C119Sn)
406 Hz, Me2Sn), 127.4 (C3), 128.4 (C4), 135.6 (C2),
140.1 (1J (CSi) 21 Hz, C1). l(Si) (CDCl3): −5.9. l(Sn)
(CDCl3) 74.6. m/z 567 (20%, (Me2PhSi)3CSnMe2=R),
489 (25, RꢀPhH), 309 (40, RꢀMe4SnꢀPhH), 247 (25,
RꢀMe3SnPhꢀPhH), 227 (25, Me2PhSn), 197 (25, PhSn),
154 (70, Ph2), 91 (70, C6H5CH2), 77 (55, Ph), 73 (50,
Me3Si).
2
0.84 (18H, s, J (HSi) 6.2 Hz, Me2Si), 7.0–7.6 (15H, m,
Ph). l(C) (CDCl3) 4.7 (s, 3J(CSn), 14.7 Hz, Me2Si),
127.8 (C3), 129.7 (C4), 135.9 (C2), 136.6 (C1). l(Si)
(CDCl3): −5.0. l(Sn) (CDCl3): −56.5. m/z 627 (2%,
MꢀMe), 591 (3, MꢀMeꢀHCl), 402 (30, MꢀMeSnCl3),
325 (25, MꢀPhꢀMeSnCl3), 309 (40), 197 (30),, 175 (25),
135 (100), 105 (30), 73 (30), 43 (30). A second product
began to crystallise out after 3 h as colourless needles
and was identified as chloro{tris(dimethylphenyl-
silyl)}methane, (Me2PhSi)3CCl (2.5 g, 46%), m.p.
199°C.(lit. [25] 201°C) Anal. found: C, 66.6; H, 7.4.
3.23. Reaction of (Me2PhSi )3CSnMe2Cl with LiAlH4
A solution of (Me2PhSi)3CSnMe2Cl (2.0 g, 3.3 mmol)
in dry THF (10 cm3) was added to a solution of LiAlH4
(0.15 g, 3.9 mmol) in THF (10 cm3) under nitrogen, and
the mixture was stirred for 1 h. The solvent was then
removed and the residue extracted with anhydrous
toluene. The toluene was evaporated from the extract
and the residue was recrystallised from hexane and
1
shown
to
be
tris(dimethylphenylsilyl)methane,
C25H33ClSi3. Calc.: C, 66.4; H, 7.3%. The H, 13C and
(Me2PhSi)3CH, (1.2 g, 87%), m.p. 103°C (lit. [19],
29Si NMR and mass spectra were identical with those
recorded previously [26].
1
105°C). H NMR (C6D6): 0.25 (18H, s, Me2Si), 0.53

224
S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
3.26. Preparation of Bu3SnOEt
destroy the residual PhLi. The solvent was removed
and the residue was extracted into CH2Cl2 (50 cm3).
The extract was filtered, the solvent was pumped away
from the extract and the white residue was recrys-
tallised from MeOH to give (Me3Si)2C(SnMe2Ph)2 (1.80
g, 78%) m.p. 115°C. Anal. found: C, 41.6; H, 7.5
C23H40Si2Sn2. Calc.: C, 41.2; H, 7.8%. l(H) (CH2Cl2)
Sodium (0.15 g, 6.5 mmol) was cautiously dissolved
in anhydrous EtOH (10 cm3) and a solution of Bu3SnCl
(2.0 g, 6.1 mmol) in EtOH (10 cm3) was added. The
mixture was stirred for 2 h, the solvent then removed,
and the residue distilled at 90°C / 0.1 mmHg (Lit.
92°/0.1 mm [27]) to give tributyl(ethoxy)tin, Bu3SnOEt,
(1.9 g, 93%). l(Sn) (CCl4ꢀCDCl3 1:1) 106. The only
value given in the literature for comparison is l 86 [28],
but this is for the neat liquid which is known to be
highly associated. Shifts of 90–130 have been reported
for trialkylalkoxytins in halogenated or hydrocarbon
solvents [29].
2
0.16 (18H, s, Me3Si), 0.5 (12H, s, Me2Sn J(SnH) 49.5
Hz), 7.21–7.58 (10H, m, Ph). l(C) (CDCl3/CH2Cl2)
−3.1 (1J(CSn) 329 Hz SnMe2), 5.2 (3J(CSn) 15.9 Hz,
SiMe3), 127.8(C3) 128.1(C4), 136.6 (C2), 143.7(C1).
l(Sn) (CDCl3/CH2Cl2) −19.2. m/z 597 (30%, MꢀMe),
535 (5, MꢀPh), 385 (MꢀPhMe2Sn), 255(20), 227(20,
PhMe2Sn), 193(20), 165(20), 135(100), 73(95).
3.27. Reaction of Bu3SnOEt with ICl
3.30. Preparation of (Me3Si )2C(SnMe2Ph)Li
A solution of ICl (0.49 g, 3.0 mmol) in CCl4 (20 cm3)
was added dropwise during 10 min to a stirred solution
of Bu3SnOEt (1.9 g, 2.97 mmol) in CCl4 (10 cm3). The
mixture was stirred for a further 5 min, after which the
1H NMR spectrum showed that reaction was complete.
The solvent was removed and the residue distilled at
108–111 °C/20 mmHg to give tributylchlorostannane,
Bu3SnCl, (0.9 g, 93%). l(Sn) NMR (CCl4-20% CDCl3):
154.2. When an authentic sample of Bu3SnCl was
added, the signal was enhanced.
A 1.3 M solution of MeLi in Et2O (3.8 cm3) was
added dropwise to a solution of (Me3Si)2C(SnMe2Ph)2
(3.0 g, 4.9 mmol) in THF (20 cm3), and the mixture was
stirred at room temperature for 10 min, after which the
reaction was complete. (This was shown by adding a
sample (0.5 cm3) of the mixture to Me3SiCl (2 cm3),
1
replacing the solvent by CH2Cl2 and recording the H
NMR spectrum, in which the ratio of the integrals of
the Me3Si-signals from (Me3Si)3CSnMe2Ph and
(Me3Si)2C(SnMe2Ph)2 was \97/3.) A few drops of
Me3SiOMe were added to destroy any residual methyl-
lithium before the solution was used.
3.28. Reaction of (Me3Si )2CCl2 with two equi6alents of
Ph3SnLi
A solution of (Me3Si)2CCl2 (5 g, 21.9 mmol), in THF
(20 cm3) was added dropwise with stirring during 20
min to a solution of Ph3SnLi [30] (43.8 mmol) in THF
(50 cm3) at 0°C. The mixture was stirred for 3 h, the
solvent then removed and the solid residue recrys-
tallised from light petroleum (b.p. 60–80 °C). Initially
bis(trimethylsilyl)(triphenylstannyl)methane separated
(1.2 g, 10.7%),. m.p. 96°C. Anal. found: C, 59.0; H,
6.65. C25H34Si2Sn. Calc.: C, 58.8; H, 6.7%. l(H)
(C6D6): 0.13 (18H, s, Me3Si), 0.39 (1H, s, CH), 7.0–7.7
(15H, m, Ph). l(C) (C6D6) 0.59 (CH), 3.6 (Me3Si),
128.8 (C3), 129.1 (C4), 137.6 (C2), 141.4 (C1). l(Si)
(C6D6) 1.5. l(Sn) (C6D6) 2.1. m/z 495 (3%, MꢀMe), 433
(8, MꢀPh), 351(3, Ph3Sn),197 (10 PhSn) 167 (50), 151
(100), 135 (20), 73 (30), 43 (15). A second crop of
crystals proved to be hexaphenylditin (12 g, 71%), m.p.
225 °C (lit. 229.5–231°C [30,31]).
3.31. Reaction of (Me3Si )2C(SnMe2Ph)Li with
Me2SiCl2
A solution of (Me3Si)2C(SnMe2Ph)Li (4.9 mmol) in
THF (20 cm3) was added dropwise with stirring to a
solution of Me2SiCl2 (0.64 g, 5.0 mmol) in THF (10
cm3). The mixture was stirred for a further 10 min and
the solvent then removed. The residue was extracted
with CH2Cl2 (20 cm3), the solvent evaporated from the
extract, and the residue recrystallised from hexane (10
cm3) to give needle-like crystals of {(chlorodimethyl-
silyl)bis(trimethylsilyl)methyl}dimethylphenylstannane,
(1.8 g, 76%), m.p. 136°C. Anal found: C, 42.7; H, 7.35.
C17H35ClSi3Sn Calc: C, 42.7; H, 7.3%. l(H) (CDC13):
0.26 (18H, s, 2J(HSi) 6.2 Hz, Me3Si), 0.53 (s, 6H,
2
2J(HSi) 6.5 Hz, Me2Si), 0.59 (s, 6H, J(HSn) 50.6 Hz,
Me2Sn), 7.31–7.72 (5H, m, Ph). l(C) (CDCl3): −2.5
(1J(CSn) 353 Hz, Me2Sn); 5.0, (1J(CSi) 51.7 Hz,
Me3Si), 8.5 (Me2Si), 127.9 (C3), 128.3 (C4) 136.9 (C2),
143.2 1J(CSn) 470 Hz, (C1). d(Si) (CDCl3): −0.6
(Me3Si), 27.9 (Me2Si). l(Sn) (CDCl3): −33.4. m/z 463
(28%, MꢀMe), 427 (22, MꢀMeꢀHCl), 263 (40,
Me2SiꢁC(SiMe3)SiMePh), 248 (15), 227 (15), 201 (100,
Me2SiꢁC(SiMe3)SiMe2), 135 (10), 73 (60), 58 (10).
3.29. Preparation of (Me3Si )2C(SnMe2Ph)2 [32]
A solution of PhLi (8.5 mmol) in Et2O (10 cm3) was
added
dropwise
to
a
stirred
solution
of
(Me3Si)2C(SnMe2Cl)2 [5] (2.0 g 3.8 mmol) in THF (20
cm3) at room temperature. The mixture was stirred for
1 h and then treated with a few drops of MeOH to

S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
225
3.32. Reaction of (Me3Si )2C(SnMe2Ph)(SiMe2Cl) with
AgBF4
The molecule had two different orientations with
occupancies 0.72 and 0.28.
A solution of (Me3Si)2C(SnMe2Ph)(SiMe2Cl) (0.50 g,
1.05 mmol) in CH2Cl2 (10 cm3) was added in one
portion to AgBF4 (0.2 g, 1.03 mmol) in CH2Cl2 (10
cm3) and the mixture was stirred for 24 h. The 1H
NMR spectrum showed that only the starting material
was present. The mixture was heated under reflux for
20 min and then filtered. The solvent was removed from
the filtrate and the residue recrystallised from hexane
(10 cm3) to give fluoro{(fluorodimethylsilyl)bis
(trimethylsilyl)methyl}dimethylstannane (90.4 g, 96%),
m.p. 198°C. Anal. found: C, 32.9; H, 7.6.
C11H30F2Si3Sn. Calc.: C, 32.7; H, 7.4%. l(H) (CDCl3):
0.25 (18H, s, 2J(HSi) 6.1 Hz, Me3Si), 0.43 (6H, d,
4.2. TpsiSnMeCl2, 2
Crystal data: C26H36Cl2Si3Sn, monoclinic, P21/c,
M=622.4, a=11.151(5), b=17.766(6), c=15.074(7)
3
−
˚
˚
A, i=95.38(3)°, U=2972.9 A , Z=4, Dc=1.4 g cm
3, F(000)=1272, monochromated Mo-Kh radiation,
−1
˚
u=0.71069 A, v=11.7 cm
.
A crystal of dimensions 0.20×0.35×0.20 mm was
used for data collection at 21°C on an Enraf-Nonius
CAD-4 diffractometer. A total of 5686 reflections with
h k9l and 2Bq B25° were measured by a q/2q scan
with scan width Dq=(0.8+0.35 tan q)° and a maxi-
mum scan time of 1 min. Corrections were made for
Lorentz and polarization effects and for absorption
using DIFABS (max 1.22, min 0.72). 2846 reflections
with ꢀF2ꢀ\|(F2) were used in the refinement, where
|(F2)=[|2(I)+(0.04I)2]1/2/Lp.
The heavy atom routines of the SHELX-86 program
were used to locate non-hydrogen atoms which were all
refined by full-matrix least squares with anisotropic
thermal parameters using programs from the Enraf-No-
nius SDP package. The Cl and Me groups of the
SnMeCl2 entity showed evidence of disorder, and a
refinement of occupancies suggested that the site la-
belled Cl(2) was in fact 0.64Cl and 0.36C while the site
C(26) was 0.36Cl and 0.64C, and appropriate average
scattering factors were used. The H atoms of the Tpsi
3
3J(HF) 7.5 Hz, Me2Si), 0.70 (d, 6H, J(HF) 3.8 Hz,
2J(HSn) 55 Hz, Me2Sn,). l(C) (CDC13): 4.1 (Me3Si),
4.3 (Me2Si), 4.5 (Me2Sn). l(Si) (CDCl3): −1.9 (d,
3J(SiF) 4.9 Hz, Me3Si)., −28.4 (d, 1J(SiF) 281 Hz,
1
SiMe2F). l(Sn) (CDCl3): 146.8 (dd, J(SnF) 2376 Hz,
3
3J(SnF) 65.5 Hz). l(F) (CDCl3): −140.4 (sept, J(FH)
1
7.5 Hz, J(FSi) 283 Hz, SiF), −204.7 (sept unresolved,
1J (F119Sn) 2379 1J(F117Sn) 2272 Hz, 2J(FC) 65 Hz,
SnF). m/z 389 (40%, MꢀMe), 209 (100, MꢀMe4SnꢀMe),
165 (35, Me3Sn), 135 (17, MeSn), 73 (35, Me3Si).
4. Crystal structure determinations
4.1. [{(Me3Si )3C}Me(O2NO)Sn]2O, 1
group were fixed at calculated positions with Uiso=
1.3Ueq for the atoms to which they were bonded. The H
atoms on C(26) were omitted. The final parameters
were R=0.061, R%=0.056, s=1.4, number of vari-
ables=289, number of observed reflections=2846,
Crystal data: C22H60N2O7Si6Sn2, monoclinic, C2/c,
M=870.7, a=14.397(9), b=10.599(4), c=26.798(28)
3
˚
˚
A, i=93.29(7)°, U=4082.3 A , Z=4, Dc=1.41 g
cm−3, F(000)=1784, monochromated Mo-Kh radia-
w=|−2(F), S w(ꢀFoꢀ−ꢀFcꢀ)2 minimized, (D/|)max
=
−1
−3
˚
˚
tion, u=0.71069 A, v=14.34 cm
.
0.02, (Dz)max,min=0.54, −0.46 e A
A crystal of dimensions 0.43×0.15×0.2 mm was
used for data collection at 21°C on an Enraf-Nonius
CAD-4 diffractometer. A total of 3944 reflections with
+h+k 9l and 2Bq B25° were measured by a q/2q
scan. Corrections were made for Lorentz and polariza-
tion effects. There was no decay during data collection.
After averaging of equivalent reflections (Rint=0.025)
there were 3804 unique relections of which 2584 with
ꢀF2ꢀ\3|(F2) were used in the refinement, where
|(F2)=[|2(I)+(0.04I)2]1/2/Lp.
4.3. TpsiSnCl3 3
(
Crystal data: C25H33Cl3Si3Sn, trigonal P3, a=
3
˚
˚
14.910(4), c=11.321(3) A, U=2179.6 A , Z=3, Dc=
1.50 g cm−3, F(000)=978. Monochromated Mo-Kh
radiation, u=0.71069 A, v=12.9 cm−1. Reflections
˚
from a crystal 0.2×0.2×0.2 mm were indexed on the
basis of the trigonal cell above; weaker reflections with
a different profile could be indexed with a larger cell
˚
The SHELXS-86 program (Patterson method) was
used to locate the Sn atom, and difference maps were
used to find the remaining non-hydrogen atoms, which
were refined by full-matrix least squares with an-
isotropic factors except for O(2a), O(3a), O(4a), N(a),
C(8a), C(10a) and C(11a), which were left isotropic.
The hydrogen atoms were omitted. The final parame-
ters were R=0.074, R%=0.096, observed reflections=
with the same c axis and a=25.81 A. 4032 relections
with h, 9k, l and 2BqB25° were measured and 1514
2
with ꢀFꢀ \3|(F2) were used. By direct methods
(SHELXS-86) in space group P3 three independent
molecules, two ordered and one disordered, were lo-
cated. The space group was changed to P3 with one
molecule disordered across an inversion centre and the
other in a general positon. All the atoms were refined
by full matrix least squares with anisotropic tempera-
(
2584, w=|(F)−2
.

226
S.S. Al-Juaid et al. / Journal of Organometallic Chemistry 564 (1998) 215–226
[9] (a) C. Walling, A. Padwa, J. Am. Chem. Soc., 85 (1963) 1593;
(b) D.R.H. Barton, W.D. Hollis (eds.),Comphrehensive Organic
Chemistry, vol. 1, Pergamon Press, Oxford, 1979, p. 877.; (c)
B.M. Trost, I. Fleming (eds.), Comphrehensive Organic Synthe-
sis, vol. 7, Pergamon Press, Oxford, 1991, p. 41.
[10] S.M. Dhaher, C. Eaborn, J.D. Smith, J. Chem. Soc. Chem.
Commun. (1987) 1337.
ture factors except for C(1), C(1a), C(3a) and C(8a)
which were isotropic. Hydrogen atoms in molecule 1
˚
were at calculated postions (CꢀH 0.95A) and Biso
=
1.3Beq for the adjacent atom and those in molecule 2
were omitted. Refinement converged at R=0.067,
R%=0.089.
[11] C. Eaborn, D.E. Reed, J. Chem. Soc. Perkin Trans. 2 (1985)
1687.
[12] P.G. Harrison, M.J. Begley, K.C. Molloy, J. Organomet. Chem.
186 (1980) 213.
[13] See [7] and the references therein.
5. Supplementary data
[14] C.D. Garner, D. Sutton, S.C. Wallwork, J. Chem. Soc. (A)
(1967) 1949.
[15] A.M. Domingos, G.M. Sheldrick, J. Chem. Soc. Dalton. Trans.
(1974) 475.
[16] C. Glidewell, D.C. Liles, Acta Crystallogr. Sect. B 34 (1978)
1693.
For all structures, hydrogen atom coordinates, an-
isotropic thermal parameters, and complete lists of
bond lengths and angles have been deposited at the
Cambridge Crystallographic Data Centre.
[17] (a) J.A. Zubieta, J.J. Zuckerman, Prog. Inorg. Chem. 24 (1978)
251; (b) P.T. Greene, R.F. Bryan, J. Chem. Soc. (A) (1971) 2549.
[18] M.J.S. Gynane, M.F. Lappert, S.J. Miles, A.J. Carty, N.J.
Taylor, J. Chem. Soc. Dalton. Trans. (1977) 2009.
[19] C. Eaborn, P.B. Hitchcock, P.D. Lickiss, J. Organometal. Chem.
269 (1984) 235.
[20] J.L. Atwood, S.G. Bott, C. Eaborn, M.N.A. El-Kheli, J.D.
Smith, J. Organometal. Chem. 294 (1985) 23.
[21] C. Eaborn, M.N.A. El-Kheli, P.B. Hitchcock, J.D. Smith, J.
Chem. Soc. Chem. Commun. (1984) 1673.
Acknowledgements
We thank the SERC (now EPSRC) for supporting
this work and the Governments of Iraq and Saudi
Arabia for scholarships to M. Al-Rawi and S.S. Al-
Juaid, respectively.
[22] A.G. Avent, S.G. Bott, J.A. Ladd, P.D. Lickiss, A. Pidcock, J.
Organomet. Chem. 427 (1992) 9.
[23] C. Eaborn, P.B. Hitchcock, J.D. Smith, A.C. Sullivan, J. Chem.
Soc. Chem. Commun. (1983) 827.
References
[1] F. Glockling, P. Harriott, W-K. Ng, J. Chem. Res. (1979) (S) 12:
(M) 275.
[24] C. Eaborn, P.B. Hitchcock, J.D. Smith, A.C. Sullivan, J. Chem.
Soc. Chem. Commun. (1983) 1390.
[2] F. Glockling, W-K. Ng, J. Chem. Res. (1980) (S) 230; (M) 3128.
[3] F. Glockling, W-K. Ng, J.Chem. Soc. Dalton Trans. (1981)
1101.
[4] I.V. Borisova, N.N. Zemlyanskii, N.D. Kolosova, Ya.A.
Ustynyuk, I.P. Beletskaya, Izv. Akad. Nauk, Ser, Khim. (1979)
2397.
[25] G. Fritz, U. Finke, Z. Anorg. Allg. Chem. 430 (1977) 121.
[26] S.S. Al-Juaid, S.M. Dhaher, C. Eaborn, P.B. Hitchcock, C.A.
McGeary, J.D. Smith, J. Organomet. Chem. 366 (1989) 39.
[27] A.G. Davies, P.R. Palan, S.C. Vasishtha, Chem. Ind. (Lond.)
(1967) 229
[28] P.J. Smith, R.F.M. White, L. Smith, J. Organomet. Chem. 40
(1972) 341.
[5] S.M. Dhaher, C. Eaborn, J.D. Smith, J. Organomet. Chem. 355
(1988) 33.
[29] B. Wrackmeyer, Annu. Rep. NMR Spectrosc. 16 (1985) 73.
[30] H Gilman, O.L. Marrs, S-Y Sim, J. Org. Chem. 27 (1962) 4232.
[31] G.A. Razuvaev, O.S. D’yachkovskaya, I.K. Grigor’eva, N.E.
Tsyganash, Zh. Obshch. Khim. 44 (1974) 573.
[32] S.M. Dhaher, D.Phil Thesis, University of Sussex, Sussex, UK,
1986.
[6] S.S. Al-Juaid, S.M. Dhaher, C. Eaborn, P.B. Hitchcock, J.D.
Smith, J. Organomet. Chem. 325 (1987) 117.
[7] S.S. Al-Juaid, M. Al-Rawi, C. Eaborn, P.B. Hitchcock, J.D.
Smith, J. Organomet. Chem. 446 (1993) 161.
[8] A.N. Fenster, E.I. Becker, J. Organomet. Chem. 11 (1968) 549.
.