Abstract
The reaction of Os
3(CO)
10(NCMe)
2 (
1) with an excess of acenaphthylene at room temperature provided the complex Os
3(CO)
10(μ-H)(μ–η
2-C
12H
7) (
2). Compound
2 contains a σ–π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound
2 was converted to the complex Os
3(CO)
9(μ-H)
2(μ
3–η
2-C
12H
6) (
3) when heated to reflux in a cyclohexane solution. Compound
3 contains a triply bridging acenaphthyne ligand. Compound
3 reacts with acenaphthylene again at 160
°C to yield four new cluster complexes: Os
4(CO)
12(μ
4–η
2:η
2-C
12H
6) (
4); Os
2(CO)
6(μ–η
4-C
24H
12) (
5); Os
3(CO)
9(μ-H)(μ
3–η
4-C
24H
13) (
6); and Os
2(CO)
5(μ–η
4-C
24H
12)(η
2-C
12H
8) (
7). All compounds were characterized crystallographically. Compound
4 is a butterfly cluster of four osmium atoms bridged by a single acenaphthyne ligand. Compounds
5 and
7 are dinuclear osmium clusters containing metallacycles formed by the coupling of two equivalents of acenaphthyne. Compound
6 is a triosmium cluster formed by the coupling of an acenaphthyne ligand to an acenapthyl group that is coordinated to the cluster through a combination of σ and π-bonding.
Os
3(CO)
10(NCMe)
2 (
1) reacts with acenaphthylene to yield the complexes Os
3(CO)
10(μ-H)(μ–η
2-C
12H
7) (
2) and Os
3(CO)
9(μ-H)
2(μ
3–η
2-C
12H
6) (
3) by a series of two CH bond cleavages on the five membered ring. Compound
3 contains a triply bridging acenaphthyne ligand. Compound
3 reacts with acenaphthylene at 160
°C to yield the cluster complexes: Os
4(CO)
12(μ
4–η
2:η
2-C
12H
6) (
4); Os
2(CO)
6(μ–η
4-C
24H
12) (
5); Os
3(CO)
9(μ-H)(μ
3–η
4-C
24H
13) (
6); and Os
2(CO)
5(μ–η
4-C
24H
12)(η
2-C
12H
8) (
7). Compounds
5 and
7 are dinuclear osmium clusters containing metallacycles formed by the coupling of two acenaphthyne groups. Compound
6 contains an acenaphthyne ligand coupled to an acenapthyl group by a CC single bond.
