Reactive p-block cations stabilized by weakly coordinating anions

Engesser, Tobias A.; Lichtenthaler, Martin R.; Schleep, Mario; Krossing, Ingo

doi:10.1039/c5cs00672d

Cited by 274 publications

(202 citation statements)

References 755 publications

(554 reference statements)

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“…This Review brings together an overview and comparison of the properties of differing classes of WCAs and their applications,w ith af ocus on synthetic and catalytic chemistry-in particular,t ransitionmetal chemistry.W hilst ac omprehensive review of p-block cations was recently presented, [1] ar eview of cationic transition-metal complexes stabilized by WCAss till appears to be absent in the literature.T herefore,w here appropriate, we focus on this area to illustrate developments in the WCA field. This Review brings together an overview and comparison of the properties of differing classes of WCAs and their applications,w ith af ocus on synthetic and catalytic chemistry-in particular,t ransitionmetal chemistry.W hilst ac omprehensive review of p-block cations was recently presented, [1] ar eview of cationic transition-metal complexes stabilized by WCAss till appears to be absent in the literature.T herefore,w here appropriate, we focus on this area to illustrate developments in the WCA field.…”

Section: Scope Of the Reviewmentioning

confidence: 99%

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: Scope Of the Reviewmentioning

confidence: 99%

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

et al. 2018

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“…Furthermore, the high donor strength of the ylide ligand was demonstrated by the stabilization of boron cations. 30 These were found to be readily available by hydride abstraction from 20 using trityl salts with weakly coordinated anions 31 or the highly Lewis acidic B(C 6 F 5 ) 3 . 32 Cation 21 and Lewis base adducts thereof were revealed to be thermally highly stable.…”

Section: Reactivity and Coordination Ability Of Metalated Ylidesmentioning

confidence: 99%

Metalated Ylides: A New Class of Strong Donor Ligands with Unique Electronic Properties

Scharf

Gessner

2017

Inorg. Chem.

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The development and design of new ligand systems with special donor properties has been essential for crucial advances made in main-group-element and transition-metal chemistry over the years. This Forum Article focuses on metalated ylides as novel ligand systems. These anionic congeners of bisylides possess likewise two lone pairs of electrons at the central carbon atom and can thus function as X,L-type ligands with strong donor abilities. This article highlights recent efforts in the isolation and application of metalated ylides with a focus on work from this laboratory. We summarize structural and electronic properties and their use in organic synthesis as well as main-group-element and transition-metal chemistry.

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“…[1,2] It is known for its robustness against electrophiles,the high steric demand, [3] and strong electron-withdrawing properties that are comparable to those of fluorine. [1,2] It is known for its robustness against electrophiles,the high steric demand, [3] and strong electron-withdrawing properties that are comparable to those of fluorine.…”

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Superacids Based on Pentafluoroorthotellurate Derivatives of Aluminum

Wiesner¹,

Gries²,

Steinhauer³

et al. 2017

Angew Chem Int Ed

100

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The new Lewis acid Al(OTeF ) and its acetonitrile adduct CH CN→Al(OTeF ) were obtained by a simple one-step synthesis in batches of up to 15 g. Al(OTeF ) and the adduct were characterized by vibrational spectroscopy (IR, Raman) and quantum-chemical calculations. Furthermore, five different salts of the new weakly coordinating anion [Al(OTeF ) ] were prepared in a two-step procedure. [Ph P][Al(OTeF ) ], Cs[Al(OTeF ) ], [Ph C][Al(OTeF ) ], as well as the protonated benzene derivatives [C H ][Al(OTeF ) ] and [C H ][Al(OTeF ) ] were characterized by low-temperature single-crystal X-ray diffraction and NMR spectroscopy. Arenium salts have rarely been characterized in the solid state and were synthesized in this work in a simplified fashion.

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Reactive p-block cations stabilized by weakly coordinating anions

Abstract: The chemistry of the p-block elements is a huge playground for fundamental and applied work.

Cited by 274 publications

References 755 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

Metalated Ylides: A New Class of Strong Donor Ligands with Unique Electronic Properties

Superacids Based on Pentafluoroorthotellurate Derivatives of Aluminum

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