The basal-edge-bridged square-pyramidal hexanuclear cluster [Ru
6(
3-H)
2(
5-
2-ampy)(
-CO)
2(CO)
14](
1; H
2ampy = 2-amino-6-methylpyridine) reacts with indene in refluxing chlorobenzene to gi
ve [Ru
7(
3-H)(
5-
2-ampy)(
-
9-C
9H
7)(
-CO)
3(CO)
11] (
2), [Ru
6(
3-H)(
5-
2-ampy)(
5-C
9H
7)(
3-CO)(
-CO)
2(CO)
11] (
3), and the known dimer [Ru
2(
5-C
9H
7)
2(
-CO)
2(CO)
2]. While the indenyl ligand of complex
2is
5:
6 edge bridging, complex
3 has a terminal
5-indenyl ligand. The hexanuclear
6-fluorene deri
vati
ve[Ru
6(
3-H)
2(
5-
2-ampy)(
6-C
13H
10)(
-CO)
2(CO)
11] (
4) has been isolated from a reaction of compound
1 with fluorene in decane at reflux temperature. Under analogous conditions, azulene reacts with
1 togi
ve [Ru
6(
5-
2-ampy)(
3-
10-C
10H
8)(
-CO)
2(CO)
10] (
5) and [Ru
4(
3-
10-C
10H
8)(CO)
9] (
6). In bothcomplexes, the azulene ligand is attached to three Ru atoms through its ten C atoms. Four complexesha
ve been isolated from reactions of acenaphthylene with complex
1 in refluxing decane: [Ru
4(
4-
2-ampy)(
-
6-C
12H
8)(
-
4-C
12H
8)(
-CO)
2(CO)
5] (
7), [Ru
6(
4-
2-ampy)(
3-
10-C
12H
8)(CO)
12] (
8), [Ru
7(
5-
2-ampy)(
4-
12-C
12H
8)(
-CO)(CO)
12] (
9), and [Ru
6(
4-
1-ampy)(
4-
12-C
12H
8)(
-CO)
2(CO)
9] (
10). Thesecompounds do not maintain the metallic skeleton of the starting complex
1 and contain acenaphthyleneligands that display unprecedented coordination modes, such as
5:
1 edge bridging (
7),
2:
2 edge bridging(
7),
6:
5:
1 triangular face capping (
8), and
5:
3:
2:
2 quadruply bridging (
9 and
10). The coordinationmode of the ampy ligand of compound
10, which has a
4-imido fragment and an uncoordinated pyridylgroup, is also unprecedented. The high temperatures required by all these reactions promote clusterdecarbonylation processes. This accounts for the obser
vation that, with few exceptions (
3,
4,
7), most ofthe reaction products contain the polycyclic hydrocarbon ligands attached to
various metal atoms throughmany carbon atoms.