Ein leichter Zugang zur nicht‐oxidierenden Lewis‐Supersäure PhF→Al(ORF)3 (RF=C(CF3)3)

Müller, Lucas O.; Himmel, Daniel; Stauffer, Julia; Steinfeld, Gunther; Slattery, John M.; Santiso‐Quiñones, Gustavo; Brecht, Volker; Krossing, Ingo

doi:10.1002/ange.200800783

Cited by 89 publications

(34 citation statements)

References 43 publications

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“…From the Lewis acid: The synthesis route starts from easily and in large scale available PhF!Al-A C H T U N G T R E N N U N G (OR F ) 3 . [76] By contrast, the pure Lewis superacid AlA C H T U N G T R E N N U N G (OR F ) 3 is temperature sensitive and decomposition is observed in CH 2 Cl 2 . [77,78] Thus, the easier to handle fluorobenzene adduct PhF!AlA C H T U N G T R E N N U N G (OR F ) 3 , MCl (M = Cu, Au), and carbon monoxide (1.2 bar) were stirred in the weakly basic polar solvent 1,2-F 2 C 6 H 4 (e r = 13.38 at 298 K) [79] for 10 h at temperatures between À15 and À20 8C.…”

Section: Resultsmentioning

confidence: 99%

A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates

Schaefer

Kraft

Reininger

et al. 2013

Chemistry A European J

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The reaction of Cu(I), Ag(I), and Au(I) salts with carbon monoxide in the presence of weakly coordinating anions led to known and structurally unknown non-classical coinage metal carbonyl complexes [M(CO)n][A] (A = fluorinated alkoxy aluminates). The coinage metal carbonyl complexes [Cu(CO)n(CH2Cl2)m](+)[A](-) (n = 1, 3; m = 4-n), [Au2(CO)2Cl](+)[A](-), [(OC)nM(A)] (M = Cu: n = 2; Ag: n = 1, 2) as well as [(OC)3Cu⋅⋅⋅ClAl(OR(F))3] and [(OC)Au⋅⋅⋅ClAl(OR(F))3] were analyzed with X-ray diffraction and partially IR and Raman spectroscopy. In addition to these structures, crystallographic and spectroscopic evidence for the existence of the tetracarbonyl complex [Cu(CO)4](+)[Al(OR(F))4](-) (R(F) = C(CF3)3) is presented; its formation was analyzed with the help of theoretical investigations and Born-Fajans-Haber cycles. We discuss the limits of structure determinations by routine X-ray diffraction methods with respect to the C-O bond lengths and apply the experimental CO stretching frequencies for the prediction of bond lengths within the carbonyl ligand based on a correlation with calculated data. Moreover, we provide a simple explanation for the reported, partly confusing and scattered CO stretching frequencies of [Cu(I)(CO)n] units.

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Section: Resultsmentioning

confidence: 99%

A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates

Schaefer

Kraft

Reininger

et al. 2013

Chemistry A European J

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“…A number of reports have described such AlÀF interactions. [35,36] It is interesting to note that transfer of a C 6 F 5 group normally proceeds from B to Al. [34] However, in 22, the presence of the phosphonium cation presumably elevates the Lewis acidity of B, as well as the steric congestion around Al.…”

Section: Bc(h)=c[p(h)tbu 2 ]A C H T U N G T R E N N U N G (Alx 3 ) (Xmentioning

confidence: 99%

Synthesis and Reactivity of Alkynyl‐Linked Phosphonium Borates

Zhao

Lough

Stephan

2011

Chemistry A European J

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The phosphine tBu(2 PC[triple bond]CH (1) was reacted with B(C(6)F(5)) to give the zwitterionic species tBu(2)P(H)C[triple bond]CB(C(6)F(5))(3) (2). The analogous species tBu(2)P(Me)C[triple bond]CB(C(6)F(5))(3) (3), tBu(2)P(H)C[triple bond]CB(Cl)(C(6)F(5))(2) (4), tBu(2)P(H)C[triple bond]CB(H)(C(6)F(5))(2) (5), and tBu(2)P(Me)C[triple bond]CB(H)(C(6)F(5))(2) (6) were also prepared. The salt [tBu(2)P(H)C[triple bond]CB(C(6)F(5))(2)(THF)][B(C(6)F(5))(4)] (7) was prepared through abstraction of hydride by [Ph(3)C][B(C(6)F(5))(4)]. Species 5 reacted with the imine tBuN=CHPh to give the borane-amine adduct tBu(2)PC[triple bond]CB[tBuN(H)CH(2)Ph](C(6)F(5))(2) (8). The related phosphine Mes(2)PC[triple bond]CH (9; Mes=C(6)H(2)Me(3)) was used to prepare [tBu(3)PH][Mes(2)PC[triple bond]CB(C(6)F(5))(3)] (10) and generate Mes(2)PC[triple bond]CB(C(6)F(5))(2). The adduct Mes(2)PC[triple bond]CB(NCMe)(C(6)F(5))(2) (11) was isolated. Reaction of Mes(2)PC[triple bond]CB(C(6)F(5))(2) with H(2) gave the zwitterionic product (C(6)F(5))(2)(H)BC(H)=C[P(H)Mes(2)][(C(6)F(5))(2)BC[triple bond]CP(H)Mes(2)] (12). Reaction of tBu(2)PC[triple bond]CB(C(6)F(5))(2), a phosphine-borane generated in situ from 5, with 1-hexene gave the species [tBu(2)PC[triple bond]CB(C(6)F(5))(2)](CH(2)CHnBu)[tBu(2)PC[triple bond]CB(C(6)F(5))(2)] (13) and subsequent reaction with methanol or hexene resulted in the formation of [tBu(2)P(H)C[triple bond]CB(C(6)F(5))(2)](CH(2)CHnBu)[tBu(2)PC[triple bond]CB(C(6)F(5))(2)](OMe) (14) or the macrocycle {[tBu(2)PC[triple bond]CB(C(6)F(5))(2)](CH(2)CH(2)nBu)}(2) (15), respectively. In a related fashion, the reaction of 13 with THF afforded the macrocycle [tBu(2)PC[triple bond]CB(C(6)F(5))(2)](CH(2)CHnBu)[tBu(2)PC[triple bond]CB(C(6)F(5))(2)][O(CH(2))(4)] (16), although treatment of tBu(2)PC[triple bond]CB(C(6)F(5))(2) with THF lead to the formation of {[tBu(2)[triple bond]CB(C(6)F(5))(2)][O(CH(2))(4)]}(2) (17). In a related example, the reaction of Mes(2)PC[triple bond]CB(C(6)F(5))(2) with PhC[triple bond]CH gave {[Mes(2)PC[triple bond]CB(C(6)F(5))(2)](CH[triple bond]CPh)}(2) (18). Compound 5 reacted with AlX(3) (X=Cl, Br) to give addition to the alkynyl unit, affording (C(6)F(5))(2)BC(H)=C[P(H)tBu(2)](AlX(3)) (X=Cl 19, Br 20). In a similar fashion, 5 reacted with [Zn(C(6)F(5))(2)]⋅C(7)H(8), [Al(C(6)F(5))(3)]⋅C(7)H(8), or HB(C(6)F(5))(2) to give (C(6)F(5))(3)BC(H)=C[P(H)tBu(2)][Zn(C(6)F(5))] (21), (C(6)F(5))(3)BC(H)=C[P(H)tBu(2)][Al(C(6)F(5))(2)] (22), or [(C(6)F(5))(2)B](2)HC=CH[P(H)tBu(2)] (23), respectively. The implications of this reactivity are discussed.

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“…[26] To explore the Lewis acidic properties of [8] + and [10] + experimentally,wedetermined the acceptor number (AN) of the cations by using the Gutmann-Beckett method, [27] which is based on the analysis of the 31 respectively,w hich are shifted to high frequency relative to that of free Et 3 PO (d =+50.7 ppm). Thus,for [8][BArF 24 ]an acceptor number of 102 was obtained which is in the range of Lewis superacids, [28] while am uch lower acceptor number of 33 was determined for [10][BArF 24 ], suggesting significantly weaker Lewis acidity. [29] Theanalysis of the bonding situation and the Lewis acidity prompted us to explore the reactivity of [8][BArF 24 ]a nd [10][BArF 24 ]w ith pyridine derivatives having different stereoelectronic properties (Scheme 2).…”

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Lewis Base Free Oxophosphonium Ions: Tunable, Trigonal‐Planar Lewis Acids

2018

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Oxophosphonium ions (R P=O) are fascinating chemical intermediates related to the well-known acylium cations (RC=O) , and comprise a tricoordinate phosphorus(V) center with a phosphorus-oxygen double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin-2-imine and imidazolin-2-olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored.

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Ein leichter Zugang zur nicht‐oxidierenden Lewis‐Supersäure PhF→Al(OR^F)₃ (R^F=C(CF₃)₃)

Cited by 89 publications

References 43 publications

A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates

A Systematic Investigation of Coinage Metal Carbonyl Complexes Stabilized by Fluorinated Alkoxy Aluminates

Synthesis and Reactivity of Alkynyl‐Linked Phosphonium Borates

Lewis Base Free Oxophosphonium Ions: Tunable, Trigonal‐Planar Lewis Acids

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