The geminal frustrated Lewis pair (FLP) (F 5 C 2 ) 3 SnCH 2 P(tBu) 2 (2)w as prepared by reacting (F 5 C 2 ) 3 SnCl with LiCH 2 P(tBu) 2 .I ti sn eutral and contains an extremely electronegatively substituted, but relatively soft (hard-soft acid-base,H SAB) acidic tin function. Its FLPtype reactivity was proven by reaction with av ariety of small molecules (CO 2 ,S O 2 ,C S 2 ,P hNCO,H Cl, (Ph 3 P)AuCl). However,itshows no reaction in H/D scrambling experiments with H 2 /D 2 mixtures and binds CO 2 reversibly,aswas observed by VT-NMR spectroscopy. Compound 2 and all its adducts were completely characterized by means of multinuclear NMR spectroscopy, elemental analysis,and X-ray diffraction experiments.
We prepared a new overcrowded tristricyclic aromatic ene (TAE) and investigated its external stimuliresponsive behavior for the switching between a closed-shell folded form and an open-shell twisted form. Upon photoirradiation, the folded form transforms into the biradical twisted form, whereas by keeping the twisted form in the dark, the reverse reaction gradually occurs at room temperature. This switchable conformational change is analyzed by means of UV−vis and electron spin resonance spectroscopies, cyclic voltammetry, density functional theory calculations, and kinetic studies. Article pubs.acs.org/joc
Anthracene-attached tricyclic aromatic hydrocarbon radicals having different central polygons, Ant-5, Ant-6, and Ant-7,w ere synthesized to evaluatet he role of an anthracene substituent group in the stabilitya nd reactivity of tricyclic aromatich ydrocarbon radicals. The bulky anthryl group effectively protects ac arbon atom with high spin density,r esultingi nh igh persistence of the radicals. On the other hand, the combination of the anthrylg roup and the tricyclica romatic scaffold makes the molecular structure drastically change from at wisted form to af olded form and an unpaired electron movesi nto the anthryl moiety,e ventually affordingatail-to-tail s-dimer.[a] Dr.
Das geminale frustrierte Lewis-Paar (FLP) (F 5 C 2 ) 3 SnCH 2 P(tBu) 2 (2)w urdem ittels der Reaktion von (F 5 C 2 ) 3 SnCl mit LiCH 2 P(tBu) 2 hergestellt. Es ist ungeladen und enthält eine extrem elektronegativ substituierte,a ber relativ weiche (HSAB) Zinn-Säurefunktion. Seine FLP-artige Reaktivitätz eigte es in Reaktionen mit einer Vielzahl kleiner Moleküle (CO 2 ,S O 2 ,C S 2 ,P hNCO,H Cl, (Ph 3 P)AuCl);i n H/D-Austauschexperimenten mit H 2 /D 2 -Gemischen ist es jedochunreaktiv.Esbindet reversibel CO 2 ,was mit VT-NMR-Spektroskopie nachverfolgt wurde.V erbindung 2 und alle ihre Addukte wurden mittels Mehrkern-NMR-Spektroskopie,E lementaranalyse und Rçntgenbeugungsexperimenten vollständig charakterisiert.
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