The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes

Richard D. Adams, Burjor Captain, Jack L. Smith

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The reaction of Os3(CO)10(NCMe)2 (1) with an excess of acenaphthylene at room temperature provided the complex Os3(CO)10(μ-H)(μ-η2 -C12H7) (2). Compound 2 contains a σ-π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound 2 was converted to the complex Os3(CO)9(μ-H) 232-C12 H6) (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: Os4(CO)12422-C12H6) (4); Os2(CO)6(μ-η4-C24 H12) (5); Os3(CO)9(μ-H)(μ 34-C24H13) (6); and Os2(CO)5(μ-η4-C24 H12)(η2-C12H8) (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.

Original languageEnglish
Pages (from-to)421-429
Number of pages9
JournalJournal of Organometallic Chemistry
Volume683
Issue number2
DOIs
StatePublished - Oct 15 2003
Externally publishedYes

Fingerprint

Osmium
osmium
Chemical activation
Ligands
activation
ligands
Butterflies
Cyclohexane
cyclohexane
Atoms
Temperature
acenaphthylene
room temperature
atoms

Keywords

  • Acenaphthylene
  • Acenapthyne
  • C-C Coupling
  • Osmium

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes. / Adams, Richard D.; Captain, Burjor; Smith, Jack L.

In: Journal of Organometallic Chemistry, Vol. 683, No. 2, 15.10.2003, p. 421-429.

Research output: Contribution to journalArticle

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abstract = "The reaction of Os3(CO)10(NCMe)2 (1) with an excess of acenaphthylene at room temperature provided the complex Os3(CO)10(μ-H)(μ-η2 -C12H7) (2). Compound 2 contains a σ-π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound 2 was converted to the complex Os3(CO)9(μ-H) 2(μ3-η2-C12 H6) (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: Os4(CO)12(μ4-η 2:η2-C12H6) (4); Os2(CO)6(μ-η4-C24 H12) (5); Os3(CO)9(μ-H)(μ 3-η4-C24H13) (6); and Os2(CO)5(μ-η4-C24 H12)(η2-C12H8) (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.",
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N2 - The reaction of Os3(CO)10(NCMe)2 (1) with an excess of acenaphthylene at room temperature provided the complex Os3(CO)10(μ-H)(μ-η2 -C12H7) (2). Compound 2 contains a σ-π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound 2 was converted to the complex Os3(CO)9(μ-H) 2(μ3-η2-C12 H6) (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: Os4(CO)12(μ4-η 2:η2-C12H6) (4); Os2(CO)6(μ-η4-C24 H12) (5); Os3(CO)9(μ-H)(μ 3-η4-C24H13) (6); and Os2(CO)5(μ-η4-C24 H12)(η2-C12H8) (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.

AB - The reaction of Os3(CO)10(NCMe)2 (1) with an excess of acenaphthylene at room temperature provided the complex Os3(CO)10(μ-H)(μ-η2 -C12H7) (2). Compound 2 contains a σ-π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound 2 was converted to the complex Os3(CO)9(μ-H) 2(μ3-η2-C12 H6) (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: Os4(CO)12(μ4-η 2:η2-C12H6) (4); Os2(CO)6(μ-η4-C24 H12) (5); Os3(CO)9(μ-H)(μ 3-η4-C24H13) (6); and Os2(CO)5(μ-η4-C24 H12)(η2-C12H8) (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.

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