9022 Singhal et al.
Asian J. Chem.
The reaction of mercuric halides and pseudohalides with
R3Sn
Cl
O
+
Hg
SnR3
Cl
bis(triaryltin) oxide (aryl = p-FC6H4) also proceeded in the
same fashion, yielded aryl mercuric halides, triaryltin halides
and diaryltin oxide.
R3 SnCl + R3SnOHgCl
(5)
Action of antimony halides on bis(triorganotin) oxides:
Metallic halides viz., antimonypentachloride has been used to
cleave metal-carbon bonds to varying extent and in the process
itself get arylated to give Ar2SbCl3 or ArSbCl2, respectively
SbCl5 readily cleave two aryl groups from tetraaryltin even at
room temperature. On the other hand SbCl3 being mild
electrophile is arylated to giveArSbCl2 under ordinary condition
R2SnO
+
RHgCl
The mechanism of the reaction with tellurium and anti-
mony derivatives may or may not be the same but on the basis
of the nature of products obtained, it is most reasonable to
assume that the reactions proceeded in the same manner as
that of mercuric salts5.
although complete arylation of Sb has also been reported1,2,10
.
Conclusion
It is therefore, not surprising that the reaction of antimony
pentachloride with (R3Sn)2O proceeded not only with the
Apart from an insight into the relative ease of cleavage of
Sn-O and Sn-C bonds, these reaction are useful to afford
organometallic derivatives of Hg, Sb, Sn and Te in excellent
yield and excellent purity in a simple step process.
specific cleavage of
bond but also with the
Sn
O Sn
removal of organic group from the tin atom takes place simul-
taneously (eqn. 2)
R3Sn-O-SnR3 + SbCl5→R2SbCl3 + R2SnO +R2SnCl2 (2)
ACKNOWLEDGEMENTS
where R= p-FC6H4.
Similarly the reaction of SbCl3 with bis(triaryltin)oxide
yielded RSbCl2, R2SnO and R3SnCl (eqn. 3)
The author are thankful to Head, Chemistry Department
for providing the necessary laboratory facilities and University
Grants Commission, New Delhi for financial assistance.
R3Sn-O-SnR3 + SbCl3→R2SnO + RSbCl2 + R3SnCl (3)
REFERENCES
where R = p-FC6H4.
Action of tellurium tetrachloride with bis(triorganotin)
oxides: Both tin-oxygen and tin-carbon bonds in bis(tri p-
fluorophenyltin) oxide were found to be prone to attack by
TeCl4. Cleavage of tin-carbon bond from RnSnR’4-n compounds
employing TeCl4 is well established and has been used as
convenient method for the preparation of organotellurium
compounds in high yield and high purity11,12. The reactions of
bis(tri p-fluorophenyltin) oxide with TeCl4 was conducted at
room temperature and in refluxing toluene, respectively, with
the immediate formation of white solid, R2SnO, in both cases
(eqn. 4):
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R3Sn-O-SnR3 + TeCl4 →R2SnO + R3SnCl + RTeCl3 (4)
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where R = p-FC6H4.
The separation of organotin halides from organotellurium
compounds does not pose much difficulty due to a significant
difference in solubilities. Orgnotin chlorides are highly soluble
in orgnanic solvents, whereas organotellurium halides are
insoluble at room temperature.
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As has been reported earlier for the reactions of bis(tri p-
fluorophenyltin) oxides with mercuric halides, the reactions
of mercuric cyanide, proceeded in the same fashion. The
intermediate R3Sn-O-Hg- is unstable, rearranges and split
itself to give diorganotin oxide and the corresponding
organomercuric compounds as shown below (eqn. 5).
12. A.G. Davies and P.J. Smith, In eds.: G. Wilkinson, F.G.A. Stone and
E.W. Abel, Tin, In Comprehensive Organometallic Chemistry I,
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