Structural characterization and bonding properties of lithium naphthalene radical anion, [Li+(TMEDA)2][C10H8˙−], and lithium naphthalene dianion [(Li+TMEDA)2C10H8−2]

Melero, Cristóbal; Guijarro, Albert; Yus, Miguel

doi:10.1039/b821119c

Cited by 34 publications

(27 citation statements)

References 21 publications

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“…Each scandium ion binds  4 to C1 through C4 (or C1A through C4A) with similar distances averaging 2.51 Å. These features are also reminiscent of those of the lithium naphthalene dianion [Li(TMEDA)]2(- 4 : 4 -C10H8) (TMEDA = tetramethylethylenediamine) (Melero et al, 2009). …”

Section: Scandium Fused-arene Complexes: Synthesis Characterizationmentioning

confidence: 68%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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Section: Scandium Fused-arene Complexes: Synthesis Characterizationmentioning

confidence: 68%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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“…The X-ray single-crystal structure study revealed that complex 2c similarly to the proline derived diamidobinaphthyl dilithium salt adopts a dimeric structure. 10e In the tetranuclear core of 2c each Li atom is bound to two nitrogen atoms of two different binaphthylamido ligands and at the same time two short contacts 29 Clear single-crystalline samples of 2d suitable for X-ray diffraction studies were obtained by slow diffusion of hexane in a THF solution at −20°C. The molecular structure of 2d is shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

LiCl-effect on asymmetric intramolecular hydroamination catalyzed by binaphthylamido yttrium complexes

et al. 2013

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Chiral alkyl or amido yttrium complexes were prepared from N-silyl- or N-cyclopentyl-substituted binaphthylamido ligands. According to the synthetic procedure, these complexes could be obtained in their neutral form or as heterobimetallic complexes in the presence of 1 equiv. LiCl. These new species were characterized by IR and NMR spectroscopies, elemental analyses and some of them by X-ray diffraction studies. Their efficiency as catalysts for the asymmetric intramolecular hydroamination was then evaluated with several substrates towards the synthesis of two pyrrolidines and a piperidine derivative. A cooperative effect between the lithium and the yttrium atoms was undoubtedly revealed. LiCl-containing complexes afforded indeed higher enantioselectivities than their salt-free counterparts and according to the structure of the chiral ligand, they were also the most active species.

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“…However, in Y 2 K 2 -biph, the energy level of the benzene π* orbitals is close enough to the energy level of the empty 4d orbitals of the yttrium(III) ion to induce a covalent bonding interaction and stabilize the high electron density of the benzene tetraanion. Indeed, the geometric parameters are almost identical for dianionic naphthalene complexes of lithium 76 and dianionic naphthalene complexes of rare-earth metals. 49 Inverse sandwich arene complexes of uranium 12,13,26,29,[65][66][67][68][69][70][71][72][73][74][75] are structurally similar to the rare-earth metal stabilized benzene tetraanion, however, most uranium complexes were found to contain a bridging benzene dianion instead of a tetraanion.…”

Section: Tetraanionic Aryl Substituted Benzene Complexesmentioning

confidence: 97%

Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: bonding, electronic structure, and comparison with actinides and other electropositive metals

Huang

Diaconescu

2015

Dalton Trans.

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Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes.

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Structural characterization and bonding properties of lithium naphthalene radical anion, [Li+(TMEDA)2][C10H8˙−], and lithium naphthalene dianion [(Li+TMEDA)2C10H8−2]

Abstract: The crystal structures of lithium naphthalene radical-anion (LiC10H8) and lithium naphthalene dianion (Li2C10H8) are reported, and their bonding properties analyzed.

Cited by 34 publications

References 21 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

LiCl-effect on asymmetric intramolecular hydroamination catalyzed by binaphthylamido yttrium complexes

Rare-earth metal π-complexes of reduced arenes, alkenes, and alkynes: bonding, electronic structure, and comparison with actinides and other electropositive metals

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