Tris(trifluoromethanesulfonyl)methide (“Triflide”) Anion:  Convenient Preparation, X-ray Crystal Structures, and Exceptional Catalytic Activity as a Counterion with Ytterbium(III) and Scandium(III)

Highly Hydrated Cations: Deficiency, Mobility, and Coordination of Water in Crystalline Nonahydrated Scandium(III), Yttrium(III), and Lanthanoid(III) Trifluoromethanesulfonates

“…[35] Also, in the dimeric hydrolysis products, [Sc(OH) 2 (OH 2 ) 5 ] 2 X 4 (X = Cl À ,Br À and PhSO 3 À ), seven oxygen atoms surround the scandium(iii) ion in monocapped trigonal prisms with mean ScÀO bond lengths of around 2.16 . [36,37] With bidentate ligands, scandium(iii) coordinates eight oxygen atoms in coordination polyhedra described as distorted dodecahedral or irregular bicapped trigonal prisms; [38] this occurs, for example, in the HSc(O 2 C 7 H 5 ) 4 compound with a mean ScÀO bond length of about 2.21 .…”

Metalltriflimidate sind bessere Katalysatoren für die organische Synthese als Metalltriflate – der Effekt eines stark delokalisierten Gegenions

“…Entsprechend dem Trend, dass die Brønsted-Acidität abzunehmen und die Lewis-Acidität zuzunehmen scheint, wenn die Zahl an elektronenziehenden Gruppen an dem Atom zunimmt, das an das labile Wasserstoffatom (Brønsted-Säure, OH > NH > CH) oder das Metallatom (Lewis-Säure, OM < NM < CM) gebunden ist, sollten Metallsalze von Tris(triflyl)methan, HC(SO 2 CF 3 ) 3 , sogar noch aktiver sein als die Triflimidate, was durch die wenigen verfügbaren Vergleichsdaten bestätigt wurde. [26,27] Während sich Metalltriflimidatsalze allgemein als aktiver erwiesen haben als ihre Triflatanaloga, muss gewährleistet sein, dass beide Lewis-Säuren nach der gleichen Methode synthetisiert wurden und dass ihr Hydratations/Solvatations-Zustand vergleichbar ist. Tatsächlich wird über die Rolle der Liganden diskutiert, insbesondere den Einfluss von Wasser auf die Aktivitäten der Lewis-Supersäuren.…”

Synthesis of N-heterocycles through cyclization-triggered tandem additions to alkynes and the study of promoters in ionic reactions.

“…Indeed, CTf3 -based cationic metals (e.g., Yb(CTf3)3) have shown good reactivity in reactions like nitration of aromatics. 59 Even though CTf3 -based cationic metal catalysts have potential to outperformance NTf2 -and OTf -based catalysts, chemists rarely use them. The obvious reason is the lack of commercial availability and the fact that they are troublesome to make.…”

“…The obvious reason is the lack of commercial availability and the fact that they are troublesome to make. 59 We propose that the laborious preparation of a catalyst containing CTf3 -or even other ideal counterions for the purposes of enhancing the reactivity is unnecessary; instead the same effect can be achieved in situ by simply using a commercial catalyst contain common counterion (e.g., OTf -), and adding to it the alkali salt of a CTf3 --(e.g., K + CTf3 -). When a salt like KCTf3 is added to reaction system, a reshuffling of ions will occur, a CTf3 -based reactive cationic species will be generated in situ and in so doing it will improve the efficiency of a reaction.…”

“…We attribute its all-around success to the fact that CTf3 -is relatively large (larger than NTf2 -) and weakly coordinating, 59 and it does not have labile metal-fluorine or metal-carbon bonds. In addition, CTf3 -is a carbon-based soft anion; this feature further enables ion reshuffling because most transition metal catalysts have a relatively soft metal center.…”