The Parent Cyclopentadienyltin Cation, Its Toluene Adduct, and the Quadruple‐Decker [Sn3Cp4]2+

Schleep, Mario; Hettich, Clarissa; Rojas, Jennifer Velázquez; Kratzert, Daniel; Ludwig, Thilo; Lieberth, Katharina; Krossing, Ingo

doi:10.1002/anie.201611351

Cited by 29 publications

(35 citation statements)

References 31 publications

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“…[276] Furthermore,it has subsequently been demonstrated that the reaction of Si(C 5 Me 5 ) 2 with the Brønsted acid [H(OEt 2 ) 2 ][Al(OR F ) 4 ] results in the formation of [Si(C 5 Me 5 )] + supported by the [Al(OR F ) 4 ] À ion. [362] Subvalent 4 ]c omplexes readily bind s-donor ligands (e.g. Thecation is formed through either halide abstraction from CpSnCl by Ag[Al(OR F ) 4 ], or by Cp abstraction from Cp 2 Sn by Me 3 SiF-Al(OR F ) 3 .F urthermore,t he reaction of [CpSn] + with Cp 2 Sn results in the formation of the quadruple decker complex in which [CpSn] + cations are attached to either end of the "neutral" Cp 2 Sn in abent cisoid arrangement.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Thecation is formed through either halide abstraction from CpSnCl by Ag[Al(OR F ) 4 ], or by Cp abstraction from Cp 2 Sn by Me 3 SiF-Al(OR F ) 3 .F urthermore,t he reaction of [CpSn] + with Cp 2 Sn results in the formation of the quadruple decker complex in which [CpSn] + cations are attached to either end of the "neutral" Cp 2 Sn in abent cisoid arrangement. [362] Subvalent [M(arene) n ] + Complex Cations (M = Ga, In): An elegant entry into low oxidation state Group 13 chemistry is the direct oxidation of gallium or indium metal by the silver salt Ag[Al(OR F ) 4 ]i na romatic solvents.T he resulting [E-(arene) n ][Al(OR F ) 4 ]c omplexes readily bind s-donor ligands (e.g. PPh 3 or P t Bu 3 )t of orm the pyramidal [Ga(PPh 3 ) 3 ] + cation, and with the more sterically demanding P t Bu 3 to form the cationic carbene analogue [Ga(P t Bu 3 ) 2 ] + .…”

Section: Angewandte Chemiementioning

confidence: 99%

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Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

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Section: Angewandte Chemiementioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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“…Ad istinction between neutral and cationic Lewisa cids has to be emphasized. Computed FIAs for beryllium, [56] borenium, [57] carbenium, [58] silylium, [38a, 59] phosphenium, [60] phosphonium, [61] zinc, [62] or other cationic species [63] exceed the threshold to LSA significantly.T he FIA of ac ationic compoundi nt he gas phase is strongly increased by charge neutralization and by electrostatic attraction. However,adamping of the FIA by the enthalpy of solvation (DH solv )i sm uch more pronounced for charged( cationic) than for neutral acids (Figure 4b).…”

Section: Cn Stretching Mode Of Acetonitrile Adductsmentioning

confidence: 99%

“…By using the Lewis acid Me 3 SiF-Al(OC(CF 3 ) 3 ) 3 ,t he fluoride-bridged anion (CF 3 ) 3 CO) 3 Al-F-Al(OC(CF 3 ) 3 ) 3 can easily be introduced as ("the least")w eakly coordinating anion. [27,63,123] The reaction of two Al(OC(CF 3 ) 3 ) 3 with one F À reveals an incomparably high FIA of 685 kJ mol À1 . [124] Al(C 6 F 5 ) 3 (FIA [29] 536 kJ mol À1 ): Al(C 6 F 5 ) 3 is one of the most extensively used Lewis superacids.…”

Section: Ageneral Classification Of Scalingm Ethodsmentioning

confidence: 99%

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Lewis Superacids: Classifications, Candidates, and Applications

Greb

2018

Chemistry A European J

264

242

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Lewis acids play a major role in all areas of chemistry. For a long time, toxic, corrosive and oxidizing SbF was considered as the strongest Lewis acid known. Lately, species significantly exceeding the Lewis acidity of SbF have been realized and were termed Lewis superacids (LSA). Prospective new candidates emerge steadily, which not only outperform SbF by their strength, but also in terms of their accessibility and ease of handling. In principle, Lewis superacids allow us to combine the outstanding activity of Brønsted superacids with the excellent selectivity of a common Lewis acid. However, the broad application of Lewis superacids in synthesis is all but popular. The present review deals with strong Lewis acids. First, it critically discusses Lewis acidity scaling methods and suggests an extended definition for Lewis superacidity. It then summarizes the properties and applications of the strongest currently known Lewis acids, indexed by the fluoride ion affinity (FIA). The supporting information contains a comprehensive list of experimentally and theoretically derived FIA data as a guide for the choice of Lewis acidic reagents/catalyst. This contribution shall encourage the search for new Lewis superacids and promote their application in non-specialized laboratories.

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Lewis Superacids

Thorwart

Greb

2021

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Lewis acids (LAs) play a prominent role in all domains of chemistry. The present contribution deals with a “super” class of LAs. As a starting point for a meaningful discussion, a more general treatise of the concept of Lewis acidity is required. Lewis acidity is a multi‐dimensional property that depends on a delicate interplay of steric and electronic factors during the interaction with a reference Lewis base or a substrate. Accordingly, various methods that gauge the strength and effectiveness of LAs on various grounds have been developed, as will be discussed in the first part of this work. Different scaling methods do not necessarily show the same trend. In turn, there is no reason to believe that one single parameter is sufficient to describe the full character of a LA. Based on the nature of the Lewis acidity scaling methods and the factors that cause the computed or measured output, a classification into “global”, “effective”, and “intrinsic” groups is made. With this framework in mind, the fluoride ion affinity (FIA) is chosen as a firm “global” parameter to discuss a broad range of LAs within the second part of this contribution. LAs that exceed the FIA of SbF 5 are termed Lewis superacids (LSAs). Accordingly, LAs that reach or exceed this threshold are collected and discussed. The clear focus is on neutral LAs of the p‐block elements, but reference will also be given for cationic Lewis acidic compounds. The majority of those compounds can be found in group 13 and for the heavier group 15 elements. Beyond, this summary touches strong Lewis acidity of d‐block metals and Lewis acidity in alternative media.

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The Parent Cyclopentadienyltin Cation, Its Toluene Adduct, and the Quadruple‐Decker [Sn₃Cp₄]²⁺

Cited by 29 publications

References 31 publications

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Lewis Superacids: Classifications, Candidates, and Applications

Lewis Superacids

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