The synthesis of [(η6-Flu∗H)Mn(CO)3]PF6, and its deprotonation to yield a novel coordination mode of fluorene

Moss, James R.; Thomas, J. A.; Cowley, Andrew R.; O’Hare, Dermot

doi:10.1016/j.jorganchem.2007.01.025

Cited by 8 publications

(3 citation statements)

References 17 publications

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“…The NMR data, however, suggest that the predicted twisted conformation of the Flu′′ ligand is rapidly interconverting. This is consistent with spectroscopic results obtained for previously reported metal complexes containing Flu′′ or Flu* …”

Section: Resultsmentioning

confidence: 99%

“…The heptamethylindenyl ligand (Ind*, C 9 Me 7 ), first synthesized in 1981, represents a potentially useful ligand that has received limited attention; for example, very few complexes of Ind* with group 4 complexes are known . The nonamethylfluorenyl ligand (Flu*, C 13 Me 9 ) was only recently reported, and its coordination chemistry is limited to late transition metals (Ru, Fe, Mn). , Studies on the few known Ind*- and Flu*-containing complexes suggest that these ligands are highly electron-donating. , …”

Section: Introductionmentioning

confidence: 99%

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Octa- and Nonamethylfluorenyl Complexes of Zr(II), Zr(IV), and Hf(IV). Investigation of Steric and Electronic Effects

Bazinet

Tilley

2008

Organometallics

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Flu*) were reacted with Zr and Hf half-sandwich complexes to generate mixed-ligand-metallocenes Cp′′Flu′′ZrCl 2 (1), Cp′′Flu*ZrCl 2 (2), and Cp*Flu*HfCl 2 (3) (Cp′′ ) 1,3-(SiMe 3 ) 2 C 5 H 3 , Cp* ) C 5 Me 5 ). Reaction of the metallocene dichlorides with MeLi yielded the dimethyl derivatives Cp′′Flu*ZrMe 2 (4) and Cp*Flu*HfMe 2 (5). Reduction of the zirconocene dichlorides in the presence of CO gas yielded the dicarbonyl derivatives Cp′′Flu′′Zr(CO) 2 ( 6) and Cp′′Flu*Zr(CO) 2 ( 7), which represent the first examples of zirconocene dicarbonyls containing a fluorenyl ligand derivative. Structural characterization of the zirconocene dichloride 2 and the dicarbonyls 6 and 7 revealed that the methylated fluorenyl ligands adopt an η 5 -coordination and display a twisted tricyclic core in each case. A spectroscopic study of a small series of zirconocene dicarbonyl analogues indicates that the methylated fluorenyl ligands are strong electron donors and similar in this regard to heptamethylindenyl (Ind*) and Cp*.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Octa- and Nonamethylfluorenyl Complexes of Zr(II), Zr(IV), and Hf(IV). Investigation of Steric and Electronic Effects

Bazinet

Tilley

2008

Organometallics

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“…We recently reported the synthesis of mixed-ligand zirconocene derivatives containing either octa- or nonamethylfluorenyl ligands (Flu′′, C 13 Me 8 H or Flu*, C 13 Me 9 ). , The large size and highly electron-donating natures of Flu′′ and Flu* should promote the generation of unsaturated metal centers and highly reactive hydride derivatives. Fluorenyl-supported zirconocene hydride complexes are of interest for investigation of the ligand’s influence on fundamental transformations such as olefin insertion, β-H elimination, and reductive elimination.…”

Section: Introductionmentioning

confidence: 99%

Octa- and Nonamethylfluorenyl Complexes of Zirconium(IV): Reactive Hydride Derivatives and Reversible Hydrogen Migration between the Metal and the Fluorenyl Ligand

Bazinet

Tilley

2009

Organometallics

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Reaction of the zirconocene dichloride Cp′′Flu*ZrCl 2 (Cp′′ ) 1,3-(SiMe 3 ) 2 C 5 H 3 , Flu* ) C 13 Me 9 ) with i BuLi ( i BuLi ) LiCH 2 CHMe 2 ) resulted in elimination of isobutylene and formation of Cp′′(η 5 :η 3 -C 13 Me 9 H)ZrH (1-syn-1,2-DHF*D), possessing an η 5 :η 3 -dihydrofluorenediyl ligand derived from a metalto-benzo ring hydride transfer. This species undergoes reversible hydride transfer and exists in equilibrium with only one of its three other possible isomers (1-syn-3,4-DHF*D). Compound 1-syn-1,2-DHF*D catalyzes the cyclization of 1,5-hexadiene to methylenecyclopentane, and its reaction with excess isobutylene leads to the elimination of isobutane and formation of the cyclometalated zirconocene isobutyl species (η 5 :η 1 -C 5 H 3 -1-SiMe 2 CH 2 -3-SiMe 3 )(η 5 -C 13 Me 9 )Zr i Bu (2). Reaction of Cp′′Flu′′ZrCl 2 with i BuLi directly generated the cyclometalated zirconocene species (η 5 :η 1 -C 5 H 3 -1-SiMe 2 CH 2 -3-SiMe 3 )(η 5 -C 13 Me 8 H)Zr i Bu (3); however, reaction of the dichloride Cp′′Flu′′ZrCl 2 with i BuLi in the presence of hydrogen generated the dihydrofluorenediyl monohydride derivative Cp′′(η 5 :η 3 -C 13 Me 8 H 2 )ZrH (4). Treatment of the cyclometalated isobutyl species 3 with H 2 led to partial hydrogenation of the Flu′′ ligand and formation of the monohydride Cp′′(η 5 :η 3 -C 13 Me 8 H 6 )ZrH ( 5), which contains a hexahydrofluorenediyl ligand. Partial hydrogenation of the Flu′′ ligand proceeded exclusively via an intramolecular pathway, as evidenced by the all-exo configuration of the methyl groups on the saturated benzo ring. Structural characterization of 1-syn-1,2-DHF*D, 2, 3, and 5 revealed a highly strained η 5 :η 3 -coordination mode for the dihydro-and hexahydrofluorenediyl ligands.

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Manganese: Organometallic Chemistry

Pugh

Layfield

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This article summarizes the highlights in organomanganese chemistry published in the period 2004–2012. During this time, there has been significant progress in the field of organomanganese chemistry. Notable achievements taken from the primary literature include the isolation of two‐coordinate organometallic systems, the utilization of alkali‐metal‐containing organomanganese super‐bases for the deprotonation of aromatic compounds, and the use of alkylborylene‐ and imidazole‐containing manganese complexes for the synthesis of carbene complexes.

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The synthesis of [(η6-Flu∗H)Mn(CO)3]PF6, and its deprotonation to yield a novel coordination mode of fluorene

Cited by 8 publications

References 17 publications

Octa- and Nonamethylfluorenyl Complexes of Zr(II), Zr(IV), and Hf(IV). Investigation of Steric and Electronic Effects

Octa- and Nonamethylfluorenyl Complexes of Zr(II), Zr(IV), and Hf(IV). Investigation of Steric and Electronic Effects

Octa- and Nonamethylfluorenyl Complexes of Zirconium(IV): Reactive Hydride Derivatives and Reversible Hydrogen Migration between the Metal and the Fluorenyl Ligand

Manganese: Organometallic Chemistry

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