The carboxylate-bridged polymer [{Ru2[µ-η2-OC(R)O] 2(CO)4}n] (R = H, Me or Et) as a synthon in the synthesis of dinuclear phosphorus pyridyl-, quinolyl- and bipyridyl-bridged derivatives of ruthenium(I)
Abstract
Treatment of
[{Ru
2
[µ-η
2
-OC(R)O]
2
(CO)
4
}
n
] or its acetonitrile
adduct
[Ru
2
{µ-η
2
-OC(R)O}
2
(CO)
4
(MeCN)
2
] (R = H, Me or
Et) with a two-fold molar equivalent of the phosphorus–nitrogen
ligands 2-diphenylphosphinopyridine (dppy), 2-diphenylphosphinoquinoline
(dpquin) and 6-diphenylphosphino-2,2′-bipyridine (dpbipy) in
alcohol under reflux resulted in the formation of dinuclear products of
the type
[Ru
2
{µ-η
2
-OC(R)O}
2
(CO)
4
(PPh
2
R′)
2
]
(R′ = pyridyl, quinolyl or bipyridyl) in which the
PPh
2
R′ ligands are monodentate, co-ordinating axially
through the phosphorus donor atoms, as established X-ray
crystallographically for
[Ru
2
{µ-η
2
-OC(Me)O}
2
(CO)
4
(dppy)
2
]. On the other hand reaction
of
[{Ru
2
[µ-η
2
-OC(R)O]
2
(CO)
4
}
n
] with 2 molar
equivalents of dppy or dpquin in toluene under reflux in the presence of
NH
4
PF
6
and under a slight pressure of carbon
monoxide afforded products of the type
[Ru
2
{µ-η
2
-OC(R)O}(CO)
4
(µ-dppy)
2
]PF
6
or
[Ru
2
{µ-η
2
-OC(R)O}(CO)
4
(µ-dpquin)
2
]PF
6
in which
the dppy or dpquin ligands adopt the bridging co-ordination mode, this
mode of co-ordination being confirmed through a crystal structure
determination on
[Ru
2
{µ-η
2
-OC(H)O}(CO)
4
(µ-dppy)
2
]PF
6
. Reaction of
[{Ru
2
[µ-η
2
-OC(R)O]
2
(CO)
4
}
n
] with dpbipy in
n-butanol under reflux likewise afforded products, isolated as
their hexafluorophosphate salts, in which the phosphorus–nitrogen
ligands are bridging, viz.
[Ru
2
{µ-η
2
-OC(R)O}(CO)
2
(µ-dpbipy)
2
]PF
6
, the
structure of
[Ru
2
{µ-η
2
-OC(Me)O}(CO)
2
(µ-dpbipy)
2
]PF
6
being
established X-ray crystallographically.
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