Synthesis and properties of ligand-bridged dinuclear complexes containing trans-bis[o -phenylenebis(dimethylarsine)]chlororuthenium(II) centres
Abstract
The series of mononuclear salts
trans-[RuCl(pdma)
2
(L–L)]PF
6
[pdma = o-phenylenebis(dimethylarsine);
L–L = 4,4′-bipyridine (4,4′-bipy)
2, fumaronitrile (fmn) 4, di-4-pyridyl disulfide
(dpds) 9 or trans-1,2-bis(4-pyridyl)ethylene (bpe)
11] have been synthesized by reaction of
trans-[RuCl(pdma)
2
(NO)][PF
6
]
2
with 1 equivalent of NaN
3
in acetone at room temperature
followed by reflux with an excess of L–L in butan-2-one. The salt
trans-[RuCl(pdma)
2
(C
5
H
5
NS)]PF
6
6
(C
5
H
5
NS = pyridine-4-thione) was
prepared similarly by using pyridine-4-thiol, and
trans-[RuCl(pdma)
2
(C
5
H
4
NSH)]PF
6
8
(C
5
H
4
NSH = pyridine-4-thiol) was
produced upon prolonged reflux of 9 in butan-2-one. Salts
6 and 8 are readily deprotonated by aqueous NaOH to
give
trans-[RuCl(pdma)
2
(C
5
H
4
NS)]
7 and 10. The dinuclear salts
trans-[{RuCl(pdma)
2
}
2
(µ-L
–L)][PF
6
]
2
[L–L = pyrazine (pyz) 1, 4,4′-bipy
3, fmn 5 or bpe 12] have been synthesized by
reaction of
trans-[RuCl(pdma)
2
(NO)][PF
6
]
2
with 1 equivalent of NaN
3
followed by reflux with 1
equivalent of the monometallic salts
trans-[RuCl(pdma)
2
(pyz)]PF
6
, 2,
4 or 11, respectively, in butan-2-one. The dimer
trans-[{RuCl(pdma)
2
}
2
(µ-dpd
s)][I
3
]
2
13
was prepared by oxidation of 8 with iodine in Me
2
SO
at room temperature. Single-crystal structures of 1,
3, 6 and 13 have been determined, and the
extent of intermetallic electronic coupling in the dimers 1,
3, 5, 12 and 13 is assessed using
cyclic voltammetry.
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