Di-9-anthryl disulfide at 193 K

Kansikas, Jarno; Sipilä, Kaija

doi:10.1107/s0108270199012846

Cited by 2 publications

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“…Initial efforts to prepare 1-(thiolato)triptycene proceeded by analogy to the synthesis of the corresponding alcohol as described by Wolczanski et al Thus, with Lawesson’s reagent or P 2 S 5 , commercially available 9(10H)-anthracenone (Scheme , 1 ) is converted to the corresponding thione, which then readily tautomerizes to anthracene-9-thiol. When conducted in the open air, this reaction conveniently affords disulfide ( 2 ) . Disulfide 2 itself does not permit direct ingress toward the triptycenyl group, as its reaction with benzyne results in facile sulfur atom abstraction to afford predominantly anthracene accompanied by minor quantities of bis(9-anthracenyl)sulfide ( 3 , Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Structures of Cuprous Triptycylthiolate Complexes

2012

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A synthesis of 1-(thioacetyl)triptycene (5), a convenient protected form of 1-(thiolato)triptycene [STrip](-), is described, a key transformation being the high yield conversion of tert-butyl 1-triptycenyl sulfide (8) to 5 by a protocol employing BBr(3)/AcCl. Syntheses of the two-coordinate copper(I) compounds [Bu(4)N][Cu(STrip)(2)], [Bu(4)N]10, and [(Cu(IMes)(STrip)] (13) proceed readily by chloride displacement from CuCl and [Cu(IMes)Cl], respectively. Reaction of 10 with Ph(3)SiSH or Me(3)SiI produces the heteroleptic species [Cu(STrip)(SSiPh(3))](-) (11) and [Cu(STrip)I](-) (12), detected by mass spectrometry, in mixture with the homoleptic bis(thiolate) anions. Structural identification by X-ray crystallography of the ligand precursor molecules 9-(thioacetyl)anthracene (4, triclinic and orthorhombic polymorphs), tert-butyl 9-anthracenyl sulfide (7), 5, and tert-butyl 1-triptycenyl sulfide (8) are presented. Crystallographic characterization of bis(9-anthracenyl)sulfide (3), which features a C-S-C angle of 104.0° and twist angle of 54.8° between anthracenyl planes, is also given. A crystal structure of [Bu(4)N][(STrip)], [Bu(4)N]9, provides an experimental measure of 144.6° for the ligand cone angle. The crystal structures of [Bu(4)N]10 and 13 are reported, the former of which reveals an unexpectedly small C-S···S-C torsion angle of ∼41° (average of two values), which confers a near "cis" disposition of the triptycenyl groups with respect the S-Cu-S axis. This conformation is governed by interligand π···π and CH···π interactions. A crystal structure of an adventitious product, [Bu(4)N][(Cu-STrip)(6)(μ(6)-Br)]·[Bu(4)N][PF(6)], [Bu(4)N]14·[Bu(4)N][PF(6)] is described, which reveals a cyclic hexameric structure previously unobserved in cuprous thiolate chemistry. The Cu(6)S(6) ring displays a centrosymmetric cyclohexane chair type conformation with a Br(-) ion residing at the inversion center and held in place by apparent soft-soft interactions with the Cu(I) ions.

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Section: Resultsmentioning

confidence: 99%