Syntheses and structural characteristics of [2-thiaalkyl]platinum complexes with phosphorus- and nitrogen-donor ligands
Abstract
The preparation of a series of
bis(2-thiaalkyl)platinum(II) complexes,
cis-Pt(CH
2
SR)
2
L
1
2
{R = Ph,
L
1
= PPh
3
, PMe
3
,
PMe
2
Ph, PMePh
2
or
L
1
2
= dppe
[1,2-bis(diphenylphosphino)ethane], dmpe
[1,2-bis(dimethylphosphino)ethane], dcpe
[1,2-bis(dicyclohexylphosphino)ethane], dppm
[bis(diphenylphosphino)methane];
R = C
6
H
4
Me-p,
L
1
= PPh
3
, PMe
3
,
PMe
2
Ph or L
1
2
= dppe,
dmpe; R = Me,
L
1
= PPh
3
, PMe
3
,
PMePh
2
or
L
1
2
= dppe} and their
characterisation by
1
H,
13
C and
31
P NMR
spectroscopy, are described. The relative trans influence of a
range of heteromethyl ligands, CH
2
YR
n
, is
discussed [Y = S, Si, Ge, Sn and C;
R = (variously) alkyl, aryl, alkenyl or alkynyl;
n = (appropriately) 1 or 3]. Also reported are
the formation and characteristics of the dinuclear
platinum(II) species,
[Pt(CH
2
SCH
3
)(µ-CH
2
SCH
3
)
(PPh
3
)]
2
, containing bridging thiaalkyl ligands in
a six-membered dimetallacycle. Thermolytic rearrangement of
Pt(CH
2
SPh)
2
(dppe) leads to a metallacyclic
product,
![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif)
Pt(C
6
H
4
SC![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif)
H
2
)(dppe). The
syntheses and spectroscopic identification of asymmetric complexes
cis-Pt(CH
2
SR)R′(PPh
3
)
2
(R = Ph, R′ = Me,
C
6
H
4
Bu
t
-p,
CH
2
CMe
2
Ph, CH
2
SiMe
2
Ph;
R = Me,
R′ = CH
2
SiMe
3
) are also
reported, as are unsuccessful attempts to isolate related complexes
cis-Pt(CH
2
SR)
2
L
2
[L
2
= polypyridyl N donor; L =
P(OMe)
3
]. The molecular structures of
cis-Pt(CH
2
SPh)
2
(PPh
3
)
2
·0.5CH
2
Cl
2
,
[Pt(CH
2
SCH
3
)(µ-CH
2
SCH
3
)
(PPh
3
)]
2
and
cis-Pt(CH
2
SPh)(CH
3
)(PPh
3
)
2
have been determined by X-ray diffractometry. Oxidative
addition of ClCH
2
SPh to appropriate
dimethylplatinum(II) precursors has afforded two
platinum(IV) derivatives,
PtCl(CH
2
SPh)Me
2
(dmpe) and
PtCl(CH
2
SPh)Me
2
(bipy)
(bipy = 2,2′-bipyridyl), of differing
stereochemistry.
Pt(C
6
H
4
SCH
2
)(dppe). The
syntheses and spectroscopic identification of asymmetric complexes
cis-Pt(CH
2
SR)R′(PPh
3
)
2
(R = Ph, R′ = Me,
C
6
H
4
Bu
t
-p,
CH
2
CMe
2
Ph, CH
2
SiMe
2
Ph;
R = Me,
R′ = CH
2
SiMe
3
) are also
reported, as are unsuccessful attempts to isolate related complexes
cis-Pt(CH
2
SR)
2
L
2
[L
2
= polypyridyl N donor; L =
P(OMe)
3
]. The molecular structures of
cis-Pt(CH
2
SPh)
2
(PPh
3
)
2
·0.5CH
2
Cl
2
,
[Pt(CH
2
SCH
3
)(µ-CH
2
SCH
3
)
(PPh
3
)]
2
and
cis-Pt(CH
2
SPh)(CH
3
)(PPh
3
)
2
have been determined by X-ray diffractometry. Oxidative
addition of ClCH
2
SPh to appropriate
dimethylplatinum(II) precursors has afforded two
platinum(IV) derivatives,
PtCl(CH
2
SPh)Me
2
(dmpe) and
PtCl(CH
2
SPh)Me
2
(bipy)
(bipy = 2,2′-bipyridyl), of differing
stereochemistry.
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