Properties of Pt(II) complexes with a sulfur-rich dithiolate ligand having alkyl chains and of their oxidized species. The X-ray crystal structure of [NBun4]2[Pt{C6S8(C10H21)2}]
Abstract
Reactions of [NBu
n
4
]
2
[PtCl
4
] with Na
2
[C
6
S
8
R
2
] [C
6
S
8
R
2
2–
= 2-{bis(alkylthio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2–); R = C
10
H
21
, C
14
H
29
or C
18
H
37
] in methanol afforded [NBu
n
4
]
2
[Pt(C
6
S
8
R
2
)
2
]. The crystal structure of [NBu
n
4
]
2
[Pt{C
6
S
8
(C
10
H
21
)
2
}
2
] was determined by X-ray analysis. The crystal packing structure consists of columns of anion units assembled through the association of alkyl chains, where the metal-center units are separated by the bulky cations. These complexes exhibit oxidation potentials of –0.25 to +0.35 V vs. SCE. They were oxidized by bromine or iodine to yield essentially two-electron oxidized species [Pt(C
6
S
8
R
2
)
2
]
0
, with ligand-centered oxidation. The oxidized complexes (R = C
10
H
21
and C
14
H
29
) exhibit electrical conductivities (σ) of 1.4 × 10
–2
to 4.9 × 10
–2
S cm
–1
measured for compacted pellets at room temperature, while the oxidized species with R = C
18
H
37
behaves as an insulator (σ < 10
–8
S cm
–1
). Electronic states and molecular interactions of the complexes in the solid state are discussed based on EPR, XPS, electronic absorption and reflectance spectra.
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