The reaction of a dicarbomethoxydihydrofulvalene
solution with Mo(CO)6 leads to the
formation of two isomers of
(η5:η5-(C5H3CO2Me)2)Mo2(CO)6
(1 and 2). The X-ray structure
of both compounds has been determined. Reaction of 2
with LiEt3BH yields
Li2[(η5:η5-(C5H3CO2Me)2)Mo2(CO)6]
(3), and this with Hg(CN)2 results in the
insertion of Hg into the Mo−Mo bond giving
(η5:η5-(C5H3CO2Me)2)Mo2(CO)6Hg
(4). The electrochemical study of
1−4 is
reported. The two-electron reduction of 1 and
2, through an ECE mechanism, leads to the
dianions. This reduction takes place at a significantly less
negative potential than for the
unsubstituted fulvalene
(η5:η5-C10H8)Mo2(CO)6
(5) due to the electron-withdrawing properties
of the carbomethoxy substituents. The oxidation of 1
and 2 is also affected by the
substituents, taking place at a more positive potential than
5. The reduction of 4 yields
the
dianion 2
2- and liberates Hg.
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