Fluoride Abstraction Induced by Tris(pentafluoroethyl)difluorophosphorane: A Convenient Way to Synthesize Cationic N-Heterocyclic Carbene- and Cyclic (Alkyl)(amino)carbene-Ligated Copper Alkyne and Arene Complexes.

We herein report the convenient synthesis of different N-heterocyclic carbene (NHC)- and cyclic (alkyl)(amino)carbene (cAAC)-ligated copper cations using the weakly coordinating tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2F5)3PF3]-). The reaction of the fluorido complexes [(carbene)CuF] (carbene = NHC, cAACMe) 2a-2f and the tris(pentafluoroethyl)difluorophosphorane (C2F5)3PF2 in the presence of alkynes or arenes led to fluoride transfer from Cu to the phosphorane with formation of the cationic transition metal complexes [(carbene)Cu(L)]+ and the weakly coordinating counteranion [(C2F5)3PF3]- (FAP). Using this method, the complexes [(IDipp)Cu(L)]+FAP- (IDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene; L = PhC≡CPh, 4d; PhC≡CMe, 5d), [(cAACMe)Cu(L)]+FAP- (cAACMe = 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; L = PhC≡CPh, 4f; PhC≡CMe, 5f), [(SIDipp)Cu(C6Me6)]+FAP- (6e), (SIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), and [(cAACMe)Cu(C6Me6)]+FAP- (6f) have been synthesized and characterized. The complexes [(IDipp)Cu(C6Me6)]+FAP- (6d) and [(cAACMe)Cu(C6Me6)]+FAP- (6f) have been used as catalysts for the copper(I)-catalyzed cycloaddition of benzyl azide to terminal alkynes.

An easy-to-perform evaluation of steric properties of Lewis acids.

Steric and electronic effects play a very important role in chemistry, as these effects influence the shape and reactivity of molecules. Herein, an easy-to-perform approach to assess and quantify steric properties of Lewis acids with differently substituted Lewis acidic centers is reported. This model applies the concept of the percent buried volume (%V Bur) to fluoride adducts of Lewis acids, as many fluoride adducts are crystallographically characterized and are frequently calculated to judge fluoride ion affinities (FIAs). Thus, data such as cartesian coordinates are often easily available. A list of 240 Lewis acids together with topographic steric maps and cartesian coordinates of an oriented molecule suitable for the SambVca 2.1 web application is provided, together with different FIA values taken from the literature. Diagrams of %V Bur as a scale for steric demand vs. FIA as a scale for Lewis acidity provide valuable information about stereo-electronic properties of Lewis acids and an excellent evaluation of steric and electronic features of the Lewis acid under consideration. Furthermore, a novel LAB-Rep model (Lewis acid/base repulsion model) is introduced, which judges steric repulsion in Lewis acid/base pairs and helps to predict if an arbitrary pair of Lewis acid and Lewis base can form an adduct with respect to their steric properties. The reliability of this model was evaluated in four selected case studies, which demonstrate the versatility of this model. For this purpose, a user-friendly Excel spreadsheet was developed and is provided in the ESI, which works with listed buried volumes of Lewis acids %V Bur_LA and of Lewis bases %V Bur_LB, and no results from experimental crystal structures or quantum chemical calculations are necessary to evaluate steric repulsion in these Lewis acid/base pairs.

Subvalent group 13 molecules by carbene-induced hydrogen abstraction.

The N-Heterocyclic Carbene (NHC) alane and gallane adducts (NHC)·Cp*AlH2 (NHC = Me2ImMe5, iPr2ImMe6, Dipp2Im 7) and (NHC)·Cp*GaH2 (NHC = Me2ImMe8, iPr2ImMe9, Dipp2Im 10; R2Im = 1,3-di-organyl-imidazolin-2-ylidene; Dipp = 2,6 diisopropylphenyl; Me2ImMe = 1,3,4,5-tetra-methyl-imidazolin-2-ylidene; Cp* = C5Me5) were prepared either via the reaction of (AlH2Cp*)31 with the NHC or by the treatment of (NHC)·GaH2I (NHC = Me2ImMe2, iPr2ImMe3, Dipp2Im 4) with KCp*. The reaction of (AlH2Cp*)31 with the backbone saturated NHC Dipp2ImH led to NHC ring expansion instead with the formation of (RER-Dipp2ImHH2)AlCp* 12. Heating solutions of the gallium compounds 8-10 triggered reductive elimination of Cp*H and afforded Cp*GaI16. The reaction of the alane adduct (Me2ImMe)·Cp*AlH25 with cAACMe led to the insertion of cAACMe into the Al-H bond with the formation of the compound rac-(Me2ImMe)·AlHCp*(cAACMeH) rac-14. Heating a solution of rac-14 led to irreversible isomerisation with the formation of (Me2ImMe)·AlHCp*(cAACMeH) meso-14. The alane adducts (iPr2ImMe)·Cp*AlH26 and (Dipp2Im)·Cp*AlH27 react with cAACMe with the release of the NHC and formation of the exceptionally stable oxidative addition product (cAACMeH)AlHCp* 15. Reactions of the gallane adducts 8-10 with cAACMe led to reductive elimination of cAACMe-H2 and the formation of Cp*GaI16.