The dication complex trans(O,S)-[Ru(bpy)(dmso-O) 2 (dmso-S) 2 ](OTf ) 2 [1·(OTf ) 2 ; bpy = 2,2′-bipyridyl; dmso = dimethyl sulfoxide; OTf -= CF 3 SO 3 -] was obtained from the reaction of cis(Cl),cis(S)-[RuCl 2 (bpy)(dmso-S) 2 ] with Ag(OTf ) in DMSO. The crystal structure of 1·(OTf ) 2 revealed two labile dmso-O ligands and two less-labile dmso-S ligands positioned cis to each other. In DMSO, the equatorial dmso-O in 1 2+ equilibrates with its linkage isomer dmso-S to fac(S)-[Ru(bpy)(dmso-O)(dmso-S) 3 ] 2+ [1 iso 2+ ] ([1 iso 2+ ]/[1 2+ ] = 3:97 at 298 K and 33:67 IntroductionBecause of their unique photophysical and photochemical properties, polypyridyl ruthenium(II) complexes have found many applications in the fields of supramolecular, bio-inorganic, and catalytic chemistry. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Although many heteroleptic polypyridyl ruthenium(II) complexes have been synthesized and investigated, most are of the [Ru(N-N) 2 (N′-N′)] 2+ type, in which N-N and N′-N′ are bidentate ligands such as 2,2′-bipyridyl (bpy), 1,10-phenanthroline (phen), or their analogues. [15,16] The limited range of target complexes is related to the easy synthetic access to cis-[RuCl 2 (bpy) 2 ] (commercially available) and its analogue complexes. On the other hand, tris-heteroleptic ruthenium(II) complexes [Ru(N-N)(N′-N′)(N′′-N′′)] 2+ (N′′-N′′ = third bidentate ligand) are less common than [Ru(N-N) 2 (N′-N′)] 2+ , because there are no easy and useful synthetic routes to cisbis-heteroleptic polypyridyl Ru II complexes, cis-[Ru(L) 2 (N-N)-(N′-N′)] n+ (L = monodentate ligand, n = 0-2), and moreover, there are no convenient mono(N-N)Ru II complexes, [Ru(L) 4 -(N-N)] n+ , to serve as precursors for the bis-heteroleptic polypyridyl Ru II complexes.Carbonyl-based Ru II complexes such as trans(Cl)-[RuCl 2 -(N-N)(CO) 2 ] have been used as starting materials for the prepa- [a]

Dedicated to Professor Antonio Togni on the occasion of his 65th birthday Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4 + 1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4 + 1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl-or methyl-substituted indolines. The synthesis of 3trifluoromethyl indoles was also achieved described under stoichiometric conditions.

Efficient synthesis of N , O ‐heterocyclic tetra‐substituted trifluoromethyl‐3,1‐benzoxazines via a transition‐metal‐catalyzed decarboxylative intramolecular cyclization was achieved. The decarboxylation of N ‐benzoyl trifluoromethyl‐benzoxazinones generated the amide oxygen nucleophile, allowing a selective internal C 1 ‐attack on Pd‐ or Cu‐coordinated zwitterions, affording medicinally attractive tetra‐substituted vinyl‐ or ethynyl‐trifluoromethyl‐3,1‐benzoxazines. This protocol can be applied to the synthesis of perfluoroalkyl‐ and non‐fluorinated 3,1‐benzoxazines.

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Who designed the cover?Miss Mami Shibata, a Japanese painter, created the cover. She contributed 20 of our scientific cover designs, including four covers of ChemistryOpen. The original title is "the ocean of pixel," and she modified it for the cover picture. The cover image is inspired by the diversity in the ocean also in cyberspace. In the present research, we can synthesize diverse heterocyclic molecules having a trifluoromethyl group in a single step by changing the N-substitution. You can see more variations of trifluoromethyl heterocycles in several papers by our group. Please visit our website, http://www.ach.nitech.ac.jp/ organic/shibata/publications.html#01.