Fluxional behavior of Al(Et)(q′)2 (q′=2-methyl-8-quinolinolato) studied by temperature dependent 1H NMR spectroscopy

Yamamoto, Takakazu; Iijima, Takayuki

doi:10.1016/j.jorganchem.2004.04.005

Cited by 8 publications

(3 citation statements)

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“…From Arrhenius plots of ln k shown in Fig. 3, kinetic parameters of the dynamic process were estimated at DH à = 135 kJ mol À1 and DS à = 159 J K À1 mol À1 in CDCl 2 CDCl 2 and at DH à = 124 kJ mol À1 and DS à = 151 J K À1 mol À1 in DMSO-d 6 [9], respectively, at 350 K. The large DS z 350 value suggests that the rotation proceeds through partial dissociation of the q 0 ligand. Such a partial dissociation of bidentate ligands has been proposed for various dynamic processes in metal complexes [16].…”

Section: Preparation Of the Starting Complexmentioning

confidence: 99%

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Synthesis of reactive [Al(Et)(q′)2] (q′=2-methyl-8-quinolinolato) serving as a precursor of light emitting aluminum complexes: Reactivity, optical properties, and fluxional behavior of the aluminum complexes

Iijima

Yamamoto

2006

Journal of Organometallic Chemistry

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Section: Preparation Of the Starting Complexmentioning

confidence: 99%

“…Herein we report results of studies about the [Al(Et)(q 0 ) 2 ] complex 1 and photoluminescent Al complexes derived from the complex 1. Parts of the results, including synthesis of 1 [8] and fluxional behavior of 1 in a solvent (DMSO-d 6 ) [9], have been reported in communication forms.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of reactive [Al(Et)(q′)2] (q′=2-methyl-8-quinolinolato) serving as a precursor of light emitting aluminum complexes: Reactivity, optical properties, and fluxional behavior of the aluminum complexes

Iijima

Yamamoto

2006

Journal of Organometallic Chemistry

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“…12). 55 The free energies of activation for the Zr and Hf complexes, which lie in the range 63-73 kJ mol 21 , decrease with increasing steric bulk around the nitrogen atom, consistent with a weakening of the M-N bond in the ground state. The free energy of activation in [Al(Et)(2-MeOx) 2 ] is ca.…”

Section: Hemilabile Ligands Without Redundant Donor Atomsmentioning

confidence: 83%

Dynamic stereochemical rearrangements in chiral organometallic complexes

Heard

2007

Chem. Soc. Rev.

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Organometallic complexes have long been known to display a wide variety of dynamic stereochemical processes. Classic examples of such processes include the exchange of axial and equatorial environments in trigonal bipyramidal complexes, such as Fe(CO)(5), and the migration of the metal moiety round the periphery of the cyclopentadiene ring in eta(1)-bound Cp complexes. The systematic study of fluxional processes is of interest because it can not only help provide a detailed, quantitative 'picture' of the bonding between the metals and ligands involved, but it can also help to rationalise chemical reactivity patterns. The introduction of chirality into organometallic complexes, usually in the form of a non-racemic chiral ligand, has led to an explosion in the importance such species, particularly with regard to their applications in organic functional group transformations. The presence of a chiral centre can also provide an excellent spectroscopic handle on the complex in question, enabling both novel fluxional processes to be observed and new light to be shed on old (unresolved) problems. In this critical review (101 references) the literature on metal-centred fluxional rearrangements in chiral transition and main group organometallic complexes is reviewed, complementing the recent review by Faller (see reference 8).

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