Three dinuclear (nitrosyl)iron complexes containing three 1,2-di(phenyl)ethylene-1,2-dithiolate ligands have
beenprepared ([
Fe
2(NO)
2(S
2C
2R
2)
3]
0 (R = phenyl,
1a;
p-tolyl,
2a; (4-
tert-
butyl)phenyl,
3a)). Each o
f these compoundsrepresents the
first mem
ber o
f a three-mem
bered electron-trans
fer series: [Fe
2(NO)
2(S
2C
2R
2)
3]
z (
z = 0, -1,, -2).The salt [Co(Cp)
2][Fe
2(NO)
2(L
3)
3] has also
been isolated. The molecular structures o
f 2a and
3a have
been determined
by X-ray crystallography. Both neutral complexes contain two nearly linear FeNO units, one o
f which is S,S'-coordinated to two dithiolene ligands yielding a square-
based pyramidal Fe(NO)S
4 polyhedron; the second FeNOmoiety
forms two (
![](/images/entities/mgr.gi<font color=)
f">
2-S)-
bridges to the
first unit and is S,S'-coordinated to a third dithiolate radical yielding also asquare-
based pyramidal Fe(NO)S
4 polyhedron. The electronic structures o
f the neutral, monoanionic, and dianionicspecies have
been elucidated spectroscopically (UV-vis, IR, EPR, M&
ouml;ss
bauer): [{Fe
II(NO
+)}(L
bull.gif">){Fe
II(
![](/images/entities/Ndot.gi<font color=)
f">O)}(L)
2]
0(
S = 0); [{Fe
II(
![](/images/entities/Ndot.gi<font color=)
f">O)}(L
bull.gif">){Fe
II(
![](/images/entities/Ndot.gi<font color=)
f">O)}(L)
2]
1- (
S =
1/
2); and [{Fe
II(
![](/images/entities/Ndot.gi<font color=)
f">O)}(L){Fe
II(
![](/images/entities/Ndot.gi<font color=)
f">O)}(L)
2]
2- (
S = 0), where (L)
2-represents the corresponding closed-shell dithiolate dianion and (L
bull.gif">)
- is its monoanionic radical.