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Featured researches published by Ines Raabe.


Chemistry: A European Journal | 2002

PX4+, P2X5+, and P5X2+ (X: Br, I) Salts of the Superweak Al(OR)4- Anion [R: C(CF3)3].

Marcin Gonsior; Ingo Krossing; Lutz Müller; Ines Raabe; Martin Jansen; Leo van Wüllen

PX(4) (+)[Al(OR)(4)](-) (X=I: 1 a, X=Br: 1 b) was prepared from X(2), PX(3), and Ag[Al(OR)(4)] [R=C(CF(3))(3)] in CH(2)Cl(2) at -30 degrees C in 69-86 % yield. P(2)X(5) (+) salts were prepared from 2 PX(3) and Ag[Al(OR)(4)] in CH(2)Cl(2) at -30 degrees C yielding almost quantitatively P(2)X(5) (+)[Al(OR)(4)](-) (X=I: 3 a, X=Br: 3 b). The phosphorus-rich P(5)X(2) (+) salts arose from the reaction of cold (-78 degrees C) mixtures of PX(3), P(4), and Ag[Al(OR)(4)] giving P(5)X(2) (+)[Al(OR)(4)](-) (X=I: 4 a, X=Br: 4 b) with a C(2v)-symmetric P(5) cage. Silver salt metathesis presumably generated unstable PX(2) (+) cations from PX(3) and Ag[Al(OR)(4)] (X=Br, I) that acted as electrophilic carbene analogues and inserted into the Xbond;X (Pbond;X/Pbond;P) bond of X(2) (PX(3)/P(4)) leading to the highly electrophilic and CH(2)Cl(2)-soluble PX(4) (+) (P(2)X(5) (+)/P(5)X(2) (+)) salts. Reactions that aimed to synthesize P(2)I(3) (+) from P(2)I(4) and Ag[Al(OR)(4)] instead led to anion decomposition and the formation of P(2)I(5)(CS(2))(+)[(RO)(3)Al-F-Al(OR)(3)](-) (5). All salts were characterized by variable-temperature solution NMR studies (3 b also by (31)P MAS NMR), Raman and/or IR spectroscopy as well as X-ray crystallography (with the exception of 4 a). The thermochemical volumes of the Pbond;X cations are 121 (PBr(4) (+)), 161 (PI(4) (+)), 194 (P(2)Br(5) (+)), 271 (P(2)I(5) (+)), and 180 A(3) (P(5)Br(2) (+)). The observed reactions were fully accounted for by thermochemical calculations based on (RI-)MP2/TZVPP ab initio results and COSMO solvation enthalpy calculations (CH(2)Cl(2) solution). The enthalpies of formation of the gaseous Pbond;X cations were derived as +764 (PI(4) (+)), +617 (PBr(4) (+)), +749 (P(2)I(5) (+)), +579 (P(2)Br(5) (+)), +762 (P(5)I(2) (+)), and +705 kJ mol(-1) (P(5)Br(2) (+)). The insertion of the intermediately prepared carbene analogue PX(2) (+) cations into the respective bonds were calculated, at the (RI-)MP2/TZVPP level, to be exergonic at 298 K in CH(2)Cl(2) by Delta(r)G(CH(2)Cl(2))=-133.5 (PI(4) (+)), -183.9 (PBr(4) (+)), -106.5 (P(2)I(5) (+)), -81.5 (P(2)Br(5) (+)), -113.2 (P(5)I(2) (+)), and -114.5 kJ mol(-1) (P(5)Br(2) (+)).


Angewandte Chemie | 2001

P5X2+ (X = Br, I), a phosphorus-rich binary P-X cation with a C2v-symmetric P5 cage

Ingo Krossing; Ines Raabe

Insertion of the intermediately formed carbene-analogous PX24 ion (X = Br, I) into one of the P-P bonds of the P4 tetrahedron led to the P5X2+ ion - the 1st example of the previously unknown class of phosphorus-rich binary P-X cations. The crystal structure of [P5Br2]+[Al{OC(CF3)3}]- was detd. and mol. structure calcns. were performed on both the bromide and iodide analogs. [on SciFinder (R)]


Angewandte Chemie | 2004

Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates

Ingo Krossing; Ines Raabe


Angewandte Chemie | 2004

Nichtkoordinierende Anionen – Traum oder Wirklichkeit? Eine Übersicht zu möglichen Kandidaten

Ingo Krossing; Ines Raabe


Chemistry: A European Journal | 2004

Relative stabilities of weakly coordinating anions: A computational study

Ingo Krossing; Ines Raabe


Chemistry: A European Journal | 2004

From Weakly Coordinating to Non-Coordinating Anions? A Simple Preparation of the Silver Salt of the Least Coordinating Anion and Its Application To Determine the Ground State Structure of the Ag(η2-P4)2+ Cation

Angela Bihlmeier; Marcin Gonsior; Ines Raabe; Nils Trapp; Ingo Krossing


Angewandte Chemie | 2003

Structure and Characterization of CI3+[Al{OC(CF3)3}4]−; Lewis Acidities of CX3+ and BX3†

Ingo Krossing; Angela Bihlmeier; Ines Raabe; Nils Trapp


Angewandte Chemie | 2001

P5X2+ (X=Br, I), ein phosphorreiches binäres P-X-Kation mit einemC2v-symmetrischen P5-Käfig

Ingo Krossing; Ines Raabe


Journal of Fluorine Chemistry | 2004

A computational study of SbnF5n (n = 1–4): Implications for the fluoride ion affinity of nSbF5

Ingo Krossing; Jack Passmore; Ines Raabe


Angewandte Chemie | 2003

Struktur und Charakterisierung von CI3+[Al{OC(CF3)3}4]−; Lewis-Aciditäten von CX3+ und BX3†

Ingo Krossing; Angela Bihlmeier; Ines Raabe; Nils Trapp

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Angela Bihlmeier

Karlsruhe Institute of Technology

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Nils Trapp

Karlsruhe Institute of Technology

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Marcin Gonsior

Karlsruhe Institute of Technology

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Jack Passmore

University of New Brunswick

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Lutz Müller

Karlsruhe Institute of Technology

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