A new preorganized tridentate ligand bearing three indolethiolate groups. Preparation of 3∶1 subsite-differentiated Fe4S4 clusters
Abstract
1,3,5-Triethyl-2,4,6-tris(3-sulfanylindolyl[1]methyl)benzene
(TriSH
3
) has been prepared in three steps from
3-sulfanylindole and 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene.
X-Ray analysis and NMR spectroscopy demonstrated it is highly
preorganized for co-ordination to three subsites of a
Fe
4
S
4
cluster core. The clusters
[PPh
4
]
2
[Fe
4
S
4
(TriS)(Br)] and
[PPh
4
]
2
[Fe
4
S
4
(TriS)(SPh)]
were obtained by reaction of
[PPh
4
]
2
[Fe
4
S
4
(SEt)
4
] with TriSH
3
under dynamic vacuum followed by addition
of
[(Me
2
N)
2
CSSC(NMe
2
)
2
]Br
2
and substitution of bromide with PhS
-
respectively. The latter was characterized by X-ray structure analysis.
No crystallographic symmetry is imposed on the cluster anion and the
cluster core exhibits the tetragonal distortion typical of
tetrathiolate-substituted Fe
4
S
4
cores. This
implies that the trithiolate ligand TriS
3-
is
sufficiently rigid to guarantee co-ordination to a single cluster core,
while it is still flexible enough to match the preferred core
distortions.
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