Synthesis and Isolation of Polytrityl Cations by Utilizing Hexaphenylbenzene and Tetraphenylmethane Scaffolds

Rathore, Rajendra; Burns, Carrie L.; Guzei, Ilia A.

doi:10.1021/jo035598i

Cited by 88 publications

(56 citation statements)

References 39 publications

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“…This is a consequence of planar coordination about C a in [14] þ and rapid rotation about its C a -C ipso bonds. The chemical shift of the C a resonance at d 196.9 is much lower than that found in [13] þ but its Dd of 124.3 ppm is much larger and comparable to that observed for the Ph 3 COH/Ph 3 C þ system (128 ppm) [38]. The Dd for the (h 5 -C 5 H 4 )Fe carbon atoms are larger than those for (h 5 -C 5 H 4 )Co.…”

Section: The Salts [13][bf 4 ] and [14][bfmentioning

confidence: 43%

The preparation, spectroscopy, structure and electrochemistry of some [Co(η4-C4Ph4)(η5-C5H4R)] complexes

O’Donohue

McAdam

Courtney

et al. 2011

Journal of Organometallic Chemistry

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Section: The Salts [13][bf 4 ] and [14][bfmentioning

confidence: 43%

The preparation, spectroscopy, structure and electrochemistry of some [Co(η4-C4Ph4)(η5-C5H4R)] complexes

O’Donohue

McAdam

Courtney

et al. 2011

Journal of Organometallic Chemistry

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“…Bromination of all four para-positions of tetraphenylmethane (3) was achieved according to an established procedure [14]. Pure tetrakis(4-bromophenyl)methane (4) was isolated as a yellowish crystalline solid in a yield of 83%.…”

mentioning

confidence: 99%

Quantum interference distinguishes between constitutional isomers

et al. 2010

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Matter waves, as introduced by de Broglie in 1923 [1], are a fundamental quantum phenomenon, describing the delocalized center of mass motion of massive bodies and we show here their sensitivity to the molecular structure of constitutional isomers.In quantum textbooks, matter wave phenomena are often associated with the equation λ dB = h/(mv), where the de Broglie wavelength λ dB is only determined by Plancks constant h and the particles momentum p = mv. It is a common conjecture that this relation still holds for bodies of arbitrary mass, size and complexity. But what is the role of the detailed internal molecular composition if λ dB does not include any such information?As already shown before [2], the centre of mass motion can be well described by quantum delocalization and interference of each entire molecule with itself -even if the internal atoms may populate a thermal mixture of vibrational and rotational modes at a temperature of about T = 500 K. The conceptual separation of the internal and external degrees of freedom allows us to discuss two different cases:If the interaction between the molecule and its environment makes it possible, even only in principle, to retrieve position information, the initially delocalized particle will be localized and quantum interference can no longer occur [3].The second case is of particular relevance for our present experiment: All individual atoms in a given molecular structure will add up to determine its global properties, and in particular also its electrical susceptibility. The susceptibility can couple to an external electric field and thus influence the center of mass motion of the entire particle. In this way, the internal structure becomes influential for the external motion, even though the molecule remains still widely delocalized and capable of showing de Broglie interference.First experiments along this line were recently able to apply this idea to near-field interferometry for measuring the static [4] and optical [5] polarizability α stat and α opt as well as the total electric susceptibility χ tot of molecules. The latter may also contain additional information about static or time varying electric dipole moments [6]. It has therefore been suggested that different molecular conformations might eventually also be distinguished in quantum interference experiments [7].For demonstration purposes we here compare two tailor-made model compounds 1 and 2. The design * http://www.quantumnano.at; markus.arndt@univie.ac.at † marcel.mayor@unibas.ch of both is based on our recent findings in molecular electronics which showed a considerable delocalization of the π-system in rod-like oligo phenylene ethynylene (OPE) [8,9] on the one hand and a partition of the π-system by conjugation interrupting subunits like e.g. platinum complexes [10], perpendicular torsion angles [11,12] or sp 3 -carbon atoms on the other hand. The constitutional isomers 1 and 2 both have the chemical formula C 49 H 16 F 52 and an identical molecular weight of 1592 g mol −1 , but different polari...

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“…[40] All reagents were purchased from commercial sources and used without further purification: Sodium methoxide (Merck, for synthesis), copper(I) bromide (Acros Organics, 98 %), hexamethylenetetraamine (Fluka, 99 %), trifluoroacetic acid (Solvay Fluorochemicals GmbH), boron tribromide (Merck, for synthesis), [Pd 2 dba 3 ] (Alfa Aesar), HP(tBu) 3 BF 4 (Aldrich, 97 %), 4-methoxyphenylboronic acid (Alfa Aesar, 97 %+), nickel(II) acetate tetrahydrate (Acros Organics, p.a.). Tetrabromide 1 [22] and halfimine 10 [27] were synthesized as described previously.…”

Section: Methodsmentioning

confidence: 99%

“…[22] To obtain the smaller salicylaldehyde 4, 1 was first converted into the tetramethoxylated compound 2 in 57 % yield by a copper-mediated cross-coupling reaction with sodium methoxide in a solvent mixture of dimethylformamide (DMF) and methanol (Scheme 1). [23] The next step was the Duff formylation of 2 with hexamethylenetetraamine (HMTA) in anhydrous trifluoroacetic acid, which gave tetraaldehyde 3 in 80 % yield.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Synthesis of Tetrahedral Shape‐Persistent Tetranuclear Metal–salphens

Mastalerz¹,

Oppel²

2011

Eur J Org Chem

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The synthesis of two novel tetrakis(salicylaldehydes) based on a rigid tetraphenylmethane core is presented. These salicylaldehydes were used as precursors for the construction of three‐dimensional multimetallic salphens, as exemplified by the synthesis of rigid and shape‐persistent tetranuclearzinc–, nickel– and palladium–salphens with defined geometries and distances between the metal sites. The UV/Vis measurements of the tetranuclear metal complexes are presented.

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Synthesis and Isolation of Polytrityl Cations by Utilizing Hexaphenylbenzene and Tetraphenylmethane Scaffolds

Cited by 88 publications

References 39 publications

The preparation, spectroscopy, structure and electrochemistry of some [Co(η4-C4Ph4)(η5-C5H4R)] complexes

The preparation, spectroscopy, structure and electrochemistry of some [Co(η4-C4Ph4)(η5-C5H4R)] complexes

Quantum interference distinguishes between constitutional isomers

Synthesis of Tetrahedral Shape‐Persistent Tetranuclear Metal–salphens

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