A series of digold
complexes possessing two thianthrenyl ligands,
Au
2
(Thi)
2
(Ph
2
P(CH
2
)
n
PPh
2
) (Thi: 1-thianthrenyl;
1
:
n
= 1,
2
:
n
= 2,
3
:
n
= 3,
4
:
n
= 4), were prepared and characterized by crystallographic
and spectroscopic measurements. X-ray crystallography of complexes
1
and
3
revealed U-shaped structures with short
Au–Au distances [3.2171(3) Å and 3.0735(2) Å]. Complex
2
and three of the four structure-determined molecules of
complex
4
showed structures without Au–Au contacts.
UV–vis spectroscopic measurements of
1
–
4
and TD-DFT calculations of the two conformers of
1
revealed that complexes
1
and
3
in the
solution phase contained conformers with Au(I)–Au(I) interactions
in a much higher proportion than complexes
2
and
4
. As a result, complexes with diphosphine ligands containing
an odd number of methylene groups preferred structures with Au–Au
interactions in the solid state and in solution. Oxidation of
1
with 2 equiv of PhICl
2
yielded a mixture of monomeric
and dimeric thianthrenes and its dimer
via
ligand
elimination and C–C coupling, respectively.