The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes

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

doi:10.1016/j.jorganchem.2003.08.008

Cited by 15 publications

(7 citation statements)

References 28 publications

(30 reference statements)

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“…The coupling of the polycyclic system which affords these latter products may resemble the first steps in the coupling of polycyclic aromatics during the formation of buckyballs, bowls and tubes. 30 Other examples of C-H activation in unusual organic systems includes the reaction of N-(2-thienylmethylidene)-2-thienylmethylamine with Fe 2 (CO) 9 which affords a range of compounds such as the linear species 34, which may also be viewed as an isolobal analogue of [{CpFe(CO)(m-CO)} 2 ]. 31 DFT level calculations have been used to provide insight into the structural isomerism observed in cyclopentadienyl-capped clusters [Cp 4 M 4 S 4 ] 21 .…”

Section: Methodsmentioning

confidence: 99%

21 Organometallic chemistry of bi- and poly-nuclear complexes

Low

2004

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Section: Methodsmentioning

confidence: 99%

21 Organometallic chemistry of bi- and poly-nuclear complexes

Low

2004

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…As far as we know, there are only five previous publications dealing with reactivity of acenaphthylene with transition-metal carbonyl clusters. They report triruthenium and triosmium derivatives, but not clusters of higher nuclearity.…”

Section: Resultsmentioning

confidence: 98%

Reactivity of Indene, Fluorene, Azulene, and Acenaphthylene with a Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Dihydride

et al. 2007

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The basal-edge-bridged square-pyramidal hexanuclear cluster [Ru6(μ3-H)2(μ5-κ2-ampy)(μ-CO)2(CO)14] (1; H2ampy = 2-amino-6-methylpyridine) reacts with indene in refluxing chlorobenzene to give [Ru7(μ3-H)(μ5-κ2-ampy)(μ-η9-C9H7)(μ-CO)3(CO)11] (2), [Ru6(μ3-H)(μ5-κ2-ampy)(η5-C9H7)(μ3-CO)(μ-CO)2(CO)11] (3), and the known dimer [Ru2(η5-C9H7)2(μ-CO)2(CO)2]. While the indenyl ligand of complex 2 is η5:η6 edge bridging, complex 3 has a terminal η5-indenyl ligand. The hexanuclear η6-fluorene derivative [Ru6(μ3-H)2(μ5-κ2-ampy)(η6-C13H10)(μ-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 to give [Ru6(μ5-κ2-ampy)(μ3-η10-C10H8)(μ-CO)2(CO)10] (5) and [Ru4(μ3-η10-C10H8)(CO)9] (6). In both complexes, the azulene ligand is attached to three Ru atoms through its ten C atoms. Four complexes have been isolated from reactions of acenaphthylene with complex 1 in refluxing decane: [Ru4(μ4-κ2-ampy)(μ-η6-C12H8)(μ-η4-C12H8)(μ-CO)2(CO)5] (7), [Ru6(μ4-κ2-ampy)(μ3-η10-C12H8)(CO)12] (8), [Ru7(μ5-κ2-ampy)(μ4-η12-C12H8)(μ-CO)(CO)12] (9), and [Ru6(μ4-κ1-ampy)(μ4-η12-C12H8)(μ-CO)2(CO)9] (10). These compounds do not maintain the metallic skeleton of the starting complex 1 and contain acenaphthylene ligands that display unprecedented coordination modes, such as η5:η1 edge bridging (7), η2:η2 edge bridging (7), η6:η5:η1 triangular face capping (8), and η5:η3:η2:η2 quadruply bridging (9 and 10). The coordination mode of the ampy ligand of compound 10, which has a μ4-imido fragment and an uncoordinated pyridyl group, is also unprecedented. The high temperatures required by all these reactions promote cluster decarbonylation processes. This accounts for the observation that, with few exceptions (3, 4, 7), most of the reaction products contain the polycyclic hydrocarbon ligands attached to various metal atoms through many carbon atoms.

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“…The difference is the olefinic character of the 1,2-double bond of the acenaphthylene unit. Acenaphthylene itself shows this character and has yielded several π-complexes through coordination of the 1,2-double bond. − With this point of view, 1,2-dibromoacenaphthylene resembles more a vinyl halide than an aryl halide. Oxidative-addition of vinyl halides to group 10 metals has attracted attention due to the importance of group 10 metal catalyzed coupling reactions of vinyl halides. , Coordination of the vinyl halide through the C−C double bond is believed to be on the path to oxidative-addition, and Pd and Pt π-complexes that subsequently undergo oxidative-addition have been isolated or observed. ,− However, for Ni the only vinyl halide π-complexes to have been isolated are stable to oxidative-addition, − marking 2 a rare example of a Ni(0) π-complex that subsequently undergoes oxidative-addition …”

Section: Discussionmentioning

confidence: 99%

“…Acenaphthylene itself shows this character and has yielded several π-complexes through coordination of the 1,2-double bond. [41][42][43][44][45][46][47][48] With this point of view, 1,2-dibromoacenaphthylene resembles more a vinyl halide than an aryl halide. Oxidative-addition of vinyl halides to group 10 metals has attracted attention due to the importance of group 10 metal catalyzed coupling reactions of vinyl halides.…”

Section: Discussionmentioning

confidence: 99%

Nickel and Platinum 1,2-Dibromoacenaphthylene Chemistry

Begum

Sharp

2005

Organometallics

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Addition of 1,2-dibromoacenaphthylene to Ni(COD) 2 /2L gives the oxidative-addition products trans-NiL 2 (Br)(2-bromoacenaphthylen-1-yl) (L ) PEt 3 , PMe 3 ). The intermediate π-complex Ni(PMe 3 ) 2 (η 2 -1,2-dibromoacenaphthylene) is isolated at short reaction times for L ) PMe 3 . An analogous complex, Pt(PEt 3 ) 2 (η 2 -1,2-dibromoacenaphthylene), is formed in the reaction of Pt(PEt 3 ) 4 with 1,2-dibromoacenaphthylene and must be heated to induce oxidative-addition to cis-Pt(PEt 3 ) 2 (Br)(2-bromoacenaphthylen-1-yl). Isomerization to the trans isomer is achieved by further heating. Reduction of trans-Ni(PEt 3 ) 2 (Br)(2-bromoacenaphthylen-1-yl) with Na/Hg gives two different products depending on the workup. One procedure gives the Hg-bridged complex trans,trans-Ni(PEt 3 ) 2 (Br)(acenaphthylen-1,2-diyl)Hg(acenaphthylen-1,2-diyl)Ni(PEt 3 ) 2 (Br), while another procedure gives an unidentified complex that is also formed when the reduction is done with KC 8 . Reduction of trans-Ni(PEt 3 ) 2 (Br)(2bromoacenaphthylen-1-yl) with Na/Hg in the presence of alkynes yields fluoranthenes, suggesting the formation of an acenaphthylyne complex, which couples with the alkynes. A small amount of trans,trans-Pt(PEt 3 ) 2 (Br)(acenaphthylen-1,2-diyl)Hg(acenaphthylen-1,2-diyl)-Pt(PEt 3 ) 2 (Br) is obtained from the reduction of cis-Pt(PEt 3 ) 2 (Br)(2-bromoacenaphthylen-1yl) with Na/Hg with trans-Pt(PEt 3 ) 2 (Br)(2-bromoacenaphthylen-1-yl) as the major product. Reduction of trans-Pt(PEt 3 ) 2 (Br)(2-bromoacenaphthylen-1-yl) with KC 8 results in debromination of the acenaphthylenyl ring.

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The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes

Cited by 15 publications

References 28 publications

21 Organometallic chemistry of bi- and poly-nuclear complexes

21 Organometallic chemistry of bi- and poly-nuclear complexes

Reactivity of Indene, Fluorene, Azulene, and Acenaphthylene with a Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Dihydride

Nickel and Platinum 1,2-Dibromoacenaphthylene Chemistry

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