Oxygen‐Bridged Ga₂(Et)₃(OTeF₅)₃ and the Weakly Coordinating Anions [Ga(Et)(OTeF₅)₃]⁻ and [Ga(OTeF₅)₄]⁻

Abstract

Salts of the weakly coordinating anions [Ga(OTeF 5 ) 4 ] À as well as [Ga(Et)(OTeF 5 ) 3 ] À and the neutral Ga 2 (Et) 3 (OTeF 5 ) 3 were synthesized and characterized by spectroscopic methodsa nd single-crystal X-ray diffraction. Ga 2 (Et) 3 (OTeF 5 ) 3 was formed by treating GaEt 3 with pentafluoroorthotelluric acid (HOTeF 5 )a nd reacted with PPh 4 Cl and CPh 3 Cl to [PPh 4 ][Ga(Et)(OTeF 5 ) 3 ]a nd [CPh 3 ][Ga(Et)(OTeF 5 ) 3 ]. In contrast, Ag[Ga(OTeF 5 ) 4 ]w as prepared from AgOTeF 5 and GaCl 3 and was used as av ersatile startingm aterial for furtherr eactions. Starting with Ag[Ga(

Insights on the Lewis Superacid Al(OTeF5)3: Solvent Adducts, Characterization and Properties**

“… [16] Recently, we reported on a comparable molecular structure of the higher homologue gallium Et 2 Ga( μ ‐OTeF 5 ) 2 Ga(Et)(OTeF 5 ). [17] Further investigations by IR and Raman vibrational spectroscopy confirm the presence of the dimeric [Al(OTeF 5 ) 2 Me] 2 . More details can be found in the Supporting Information.…”

“…The Al−C bond distances ( d (Al1‐C1)=192.3(8) pm) are shortened when compared to the molecular structure of dimeric [AlMe 3 ] 2 , underlining the increased Lewis acidity of the Al centers in [Al(OTeF 5 ) 2 Me] 2 [16] . Recently, we reported on a comparable molecular structure of the higher homologue gallium Et 2 Ga( μ ‐OTeF 5 ) 2 Ga(Et)(OTeF 5 ) [17] . Further investigations by IR and Raman vibrational spectroscopy confirm the presence of the dimeric [Al(OTeF 5 ) 2 Me] 2 .…”

“…OTeF 5 ) 2 Ga(Et)(OTeF 5 ). [17] Further investigations by IR and Raman vibrational spectroscopy confirm the presence of the dimeric [Al(OTeF 5 ) 2 Me] 2 . More details can be found in the Supporting Information.…”

Insights on the Lewis Superacid Al(OTeF5)3: Solvent Adducts, Characterization and Properties

“…[12] Recently, a comparable molecular structure of the higher homologue gallium was reported. [13] Further investigations by IR and Raman vibrational spectroscopy confirm the presence of the dimeric [Al(OTeF5)2Me]2. More details can be found in the Supporting Information.…”

The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications

“…Favorably, the FIA value of the Lewis acid Al(OC 10 F 15 ) 3 is in the same order of magnitude as the extreme FIA values of the Lewis acids underlying the recent anions [M(OC 5 F 4 N) 4 ] − (with M = B, Al) 23 and [M (OTeF 5 ) 4 ] − (with M = Al, Ga). 31,51 As a final proof for the exceptional FIA value of Al(OC 10 F 15 ) 3 , additional DLPNO-CCSD(T)/ cc-pVQZ calculations were performed as proposed by the group of Greb. 41 The calculation at this most reliable level resulted in a FIA of 596 kJ mol −1 for the Lewis acid Al (OC 10 F 15 ) 3 and agrees within 11 kJ mol −1 to those collected in Table 2.…”