Dihalogen–halogenomethyl complexes of indium(III) X2InCH2X (X=Br, I): Simultaneous coordination of soft and hard ligands

Water‐Stable Lewis Superacids as Precursors for (Pseudo)halogenogallate and ‐indate Salts

“…The InÀ Cl bond length of 2.414(4) Å in [In(C 2 F 5 ) 3 Cl] À is comparable to that in [InMeCl 3 ] À (2.394(3) to 2.409(3) Å) [14] and between those in the anions [InCl 4 ] À (2.345(3), 2.355(3) Å) [15] and [In(mes) 3 Cl] À (2.540(3) Å, Mes = Mesityl). [16] For the bromotris(pentafluoroethyl)indate, [In(C 2 F 5 ) 3 Br] À , the InÀ Br distance of 2.5160(5) Å is similar to those in other bromoindates ([InBr 4 ] À : 2.479(2) Å, [In(CH 2 SMe 2 )Br 3 ]: 2.504(1) Å and [Br 3 In(CH 2 ) 4 InBr 3 ] 2À : 2.539(1)À 2.548(1) Å) [15,17,18] and is exceeded by those in [InMe 2 Br 2 ] À (2.644(3), 2.635(3) Å). [19] Crystal structures of iodoindates are scarce.…”

“…A comparison with these few indates reveals that the InÀ I bond of 2.8207(5) Å in [In(C 2 F 5 ) 3 I] À is longer than in [In(C 2 H 5 )I 3 ] À (2.718(1) Å) [20] and in [In(CH 2 SR 2 )I 3 ] (R=Me: 2.7107(9) Å, R=CH 2 Ph: 2.7097(6) Å). [18] These findings do not allow to assign a clear trend of the indium-halogen bonds with respect to the electron-withdrawing nature of the pentafluoroethyl group. Crystals of the fluorotris(pentafluoroethyl)indate suitable for X-ray diffraction analysis were obtained by recrystallization from dichloromethane.…”

“…The treatment of [M(C 2 F 5 ) 3 (OH 2 ) 2 ] (M=Ga, In) with potassium cyanide and [18]crown-6 in a two-phase system of diethyl ether and water leads to the corresponding cyanide salts as colorless solids (Scheme 3).…”

“…[K( [18]crown-6)][Ga(C 2 F 5 ) 3 (CN)] crystallizes in the monoclinic space group P2 1 /n with four formula units per unit cell. The average GaÀ CN distance of 1.980 Å is shorter than in [NEt 4 ][(mes)Ga(CN) 3 ] (2.003 Å) [23] and longer in comparison to [PPh 4 ][Ga(CN) 4 ] (1.970 Å).…”

“…[11][12][13] Coordination of α-fluorine atoms to the potassium ion leads to an additional elongation of the CÀ F bond (e. g. C1À F1 1.383(2) Å). In the solid state polymeric strands are observed which consist of repeating [K( [18]crown-6)][Ga(C 2 F 5 ) 3 (CN)] units. Each potassium atom is coordinated by either four α-fluorine atoms, two α-fluorine atoms and a nitrogen atom, or two nitrogen atoms and the crown ether (see Supporting Information).…”