Tantalum Porphyrin Chemistry. Synthesis and Reactivity of Organometallic Derivatives and the X-ray Crystal Structure of the Sandwich Compound [Ta(OEP)2][TaCl6]

Dawson, Denisha Y.; Brand, Holger; Arnold, John

doi:10.1021/ja00100a074

Cited by 38 publications

(17 citation statements)

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“…An efficient entry into tantalum ± porphyrin chemistry is made possible with Me 3 TaCl 2 , which reacts with 52 to form 53 (Scheme 43). [193] In contrast, salt elimination routes with TaCl 5 fail. By reaction with [PhMeNH]BPh 4 53 can be converted into 54, which may be regarded to be a porphyrin analogue of REVIEWS R. Kempe Scheme 43.…”

Section: Compounds With Metals In the High Oxidation State And The Anmentioning

confidence: 99%

Highlights in the Renaissance of Amidometal Chemistry

Kempe¹

2000

Angewandte Chemie International Edition

271

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Turning a disadvantage to an advantage: The rather disappointing reactivity of the metal - nitrogen bond in comparison to the metal - carbon bond resulted in the neglect of amidometal chemistry after its heyday at the end of the 1960s and beginning of the 1970s. Today it is precisely this disadvantage which is being applied through the use of amido ligands to produce inert complex fragments with well-defined reaction centers. In this way the chemistry of the early transition metals has been markedly enriched, and interesting alternatives to the classically regarded cyclopentadienyl ligands are now available.

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Section: Compounds With Metals In the High Oxidation State And The Anmentioning

confidence: 99%

Highlights in the Renaissance of Amidometal Chemistry

Kempe¹

2000

Angewandte Chemie International Edition

271

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“…As described above, the φ value is 36°, which is smaller than the φ value of the other chemical forms for oep complexes ( φ =45°) but slightly larger than that of the tpp analogue ( φ =30°). To date, only one crystal structure of an isostructural Ta V complex [Ta V (oep) 2 ] + has been reported . However, its φ value is 45° and different from that of [Tb III (oep) 2 ] + .…”

Section: Resultsmentioning

confidence: 99%

“…To date, only one crystal structure of an isostructuralT a V complex [Ta V (oep) 2 ] + has been reported. [45] However,i ts f value is 458 and different from that of [Tb III (oep) 2 ] + .T his difference suggestst hat the smaller f value for [Tb III (oep) 2 ] + originatesf rom the electronic communication between two oxidized ligandsw ith radial cation nature, which is discussed below.…”

Section: Details Of Crystallography For the Cationf Orm Of The Oep Comentioning

confidence: 93%

“…The f values fort he calculated structures of both compounds were 458,c onsistentw ith the experimental values. [42,45] Geometry optimizationw ith restraints on the f value to 458 for the radical and cation forms indicated that the total energy of the restrained structures is highert han that of the unrestrained structures: + 4.80 and + 4.67 kcal mol À1 for the radical and cation forms,r espectively.T he restricted structure of the radicalf orm has no imaginary frequency,w hich suggests that this structure is quasi-stable. However, the restricted structure of the cation form has two imaginary frequencies,w hich suggests itsi nstability.T hese results indicatet hat the smaller f value of the radical and cation form is primarily due to the electronic interaction in the singly and doubly oxidized ligand system,r espectively.T he electronic interaction in the oxidized double-decker complexes is also supported by f values similar to those observed in the stackedo ep cation radical dimers in the crystals( typically 25-308).…”

Section: Theoretical Calculationsmentioning

confidence: 99%

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Redox‐Driven Symmetry Change for Terbium(III) Bis(porphyrinato) Double‐Decker Complexes by the Azimuthal Rotation of the Porphyrin Macrocycles

Yamashita

Yamanaka

Sakata

et al. 2018

Chemistry An Asian Journal

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Molecular structures for three oxidation forms (anion, radical, and cation) of terbium(III) bis(porphyrinato) double-decker complexes have been systematically studied. We found that the redox state controls the azimuthal rotation angle (φ) between the two porphyrin macrocycles. For [Tb (tpp) ] (tpp: tetraphenylporphyrinato, n=-1, 0, and +1), φ decreases at each stage of the oxidation process. The decrease in φ is due to the higher steric repulsion between the phenyl rings on the porphyrin macrocycle and the β hydrogen atoms on the other porphyrin macrocycle, which results from the shorter interfacial distance between the two porphyrin macrocycles. Conversely, φ=45° for both [Tb (oep) ] and [Tb (oep) ] (oep: octaethylporphyrinato), but φ=36° for [Tb (oep) ] . Theoretical calculations suggest that the smaller azimuthal rotation angle of the cation form is due to the electronic interaction in the doubly oxidized ligand system.

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“…[193] Salzeliminierungsrouten unter Verwendung von Schema 43. CO-Insertion und -Kupplung an kationischen Tantalkomplexen.…”

Section: Verbindungen Mit Metallen Im Hohen Oxidationszustand Und Dieunclassified

Highlights der Renaissance der Amidometallchemie

Kempe¹

2000

Angewandte Chemie

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Den vermeintlichen Nachteil nutzen: Die eher enttäuschende Reaktivität der Metall‐Stickstoff‐Bindung im Vergleich zur Metall‐Kohlenstoff‐Bindung ließ die Amidometallchemie nach ihrer Blüte Ende der sechziger, Anfang der siebziger Jahre etwas in Vergessenheit geraten. Heute nutzt man genau diesen Nachteil, um durch Amidoliganden inerte Komplexfragmente mit wohldefinierten Reaktionszentren zu bilden. Dadurch wurde die Chemie der frühen Übergangsmetalle bereichert, und neben den als klassisch anzusehenden Cyclopentadienylliganden stehen interessante Alternativen zur Verfügung.

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Tantalum Porphyrin Chemistry. Synthesis and Reactivity of Organometallic Derivatives and the X-ray Crystal Structure of the Sandwich Compound [Ta(OEP)2][TaCl6]

Cited by 38 publications

References 0 publications

Highlights in the Renaissance of Amidometal Chemistry

Highlights in the Renaissance of Amidometal Chemistry

Redox‐Driven Symmetry Change for Terbium(III) Bis(porphyrinato) Double‐Decker Complexes by the Azimuthal Rotation of the Porphyrin Macrocycles

Highlights der Renaissance der Amidometallchemie

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