Treatment of a hexane solution of the complex
[Ru
6
C(CO)
17

] and 1 equivalent of the
organodiphosphine ligands
Ph
2
P(CH
2

)
n
PPh
2
(n = 1–3) produced the series of
derivatives
[Ru
6
C(CO)
15
{µ-Ph
2
P(CH
2

)
n
PPh
2

}]
1–3, respectively, in ca. 74–94% yield.
These clusters have been characterised by IR and NMR spectroscopy and in
the solid state by X-ray analyses. The three related compounds all adopt
a similar octahedral metal core geometry with the bidentate diphosphine
ligand bridging one Ru–Ru edge of the metal polyhedron. Reaction
of [Ru
6
C(CO)
17

] with
1,4-bis(diphenylphosphine)butane,
Ph
2
P(CH
2

)
4
PPh
2
,
yielded two products which differ in the mode of bonding of the
disphospine ligand, the major product
[Ru
6
C(CO)
16
{Ph
2
P(CH
2

)
4
PPh
2
-P}]
4a in
ca. 74% yield and the minor product
[Ru
6
C(CO)
15
{µ-Ph
2
P(CH
2

)
4
PPh
2
}]
4b in
ca. 10% yield.