Boratabenzene Anions C5B(CN)6(-) and C5B(CF3)6(-) and the superacidic properties of their conjugate acids.

Designing superacids: A computational study of protonated boratabenzenes and the gas-phase acidity of their conjugate acids is presented. Conjugate acids of boratabenzenes substituted with CN or CF(3) groups (see figure) are highly acidic species; the protonated hexacyanoboratabenzene and hexakis(trifluoromethyl)boratabenzene have computational gas-phase acidities of 250.5 and 276.8 kcal mol(-1), respectively.

[1]  G. Röschenthaler,et al.  Pentakis(trifluoromethyl)phenyl, a sterically crowded and electron-withdrawing group: synthesis and acidity of pentakis(trifluoromethyl)benzene, -toluene, -phenol, and -aniline. , 2008, The Journal of organic chemistry.

[2]  Z. Maksić,et al.  Rees polycyanated hydrocarbons and related compounds are extremely powerful Brønsted superacids in the gas-phase and DMSO—a density functional B3LYP study , 2008 .

[3]  I. Leito,et al.  Anions N[C(CN)2]3- and P[C(CN)2]3- and the superacidic properties of their conjugate acids , 2007 .

[4]  C. Reed,et al.  An infrared nuNH scale for weakly basic anions. Implications for single-molecule acidity and superacidity. , 2006, Journal of the American Chemical Society.

[5]  C. Reed,et al.  The structure of the strongest Brønsted acid: the carborane acid H(CHB11Cl11). , 2006, Journal of the American Chemical Society.

[6]  Z. Maksić,et al.  Strong Acidity of Some Polycyclic Aromatic Compounds Annulated to a Cyclopentadiene Moiety and Their Cyano Derivatives – A Density Functional B3LYP Study , 2005 .

[7]  R. McDonald,et al.  Cyclic boronium and borenium cations derived from borabenzene-pyridine complexes. , 2005, Chemical communications.

[8]  Haoran Sun,et al.  Anhydrous tetrabutylammonium fluoride. , 2005, Journal of the American Chemical Society.

[9]  Ingo Krossing,et al.  Relative stabilities of weakly coordinating anions: a computational study. , 2004, Chemistry.

[10]  C. Reed,et al.  Exploration of the pentacyano-cyclo-pentadienide ion, C(5)(CN)(5)(-), as a weakly coordinating anion and potential superacid conjugate base. Silylation and protonation. , 2004, Chemical communications.

[11]  I. Leito,et al.  Generalized principle of designing neutral superstrong Brønsted acids. , 2002, Journal of the American Chemical Society.

[12]  G. Herberich,et al.  Borabenzene Adducts of Ylidic Lewis Bases. Syntheses and Structures of 3,5-Me2C5H3BCH2PPh3, 3,5-Me2C5H3BCH(SiMe3)PPh3, and C5H5BN(Ph)PPh31 , 2002 .

[13]  O. Webster.  Cyanocarbons: A classic example of discovery‐driven research , 2002 .

[14]  H. Willner,et al.  Synthesis and properties of the tetrakis(trifluoromethyl)borate anion, [b(CF3)4]-: structure determination of Cs[B(CF3)4] by single-crystal X-ray diffraction. , 2001, Chemistry.

[15]  I. Leito,et al.  Gas-Phase Acidities of Some Neutral Brønsted Superacids: A DFT and ab Initio Study , 2000 .

[16]  S. Qiao,et al.  Nucleophilic Aromatic Substitution Reactions of Borabenzene-Trimethylphosphine: A Versatile Route to 1-Substituted Boratabenzenes , 1996 .

[17]  W. M. Davis,et al.  Chemistry of Borabenzene: Efficient and General Synthesis of New Neutral Borabenzene−Ligand Complexes , 1996 .

[18]  R. Taft,et al.  Superacidity of neutral Brönsted acids in gas phase , 1996 .

[19]  W. M. Davis,et al.  A Boron Analogue of Benzene: Synthesis, Structure, and Reactivity of 1-H-Boratabenzene , 1995 .

[20]  T. Wagner,et al.  Borabenzene derivatives. 21. 2,4-Pentadienylboranes as key intermediates of a novel route to boracyclohexadienes and boratabenzenes. Structure of [Li(TMPDA)](C5H5BNMe2) , 1993 .

[21]  L. Curtiss,et al.  Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint , 1988 .

[22]  R. Boese,et al.  Synthese und Strukturuntersuchung von Pyridin‐Borabenzol und Pyridin‐2‐Boranaphthalin , 1985 .

[23]  B. Penfold,et al.  Molecular conformation of hexakis(trifluoromethyl)benzene , 1976 .

[24]  F. Bickelhaupt,et al.  Attempted synthesis of dibenzo[b,e]borin (9-boraanthracene) and its formation under electron impact , 1970 .

[25]  U. Englert,et al.  Borabenzene Derivatives. 22. Synthesis of Boratabenzene Salts from 2,4-Pentadienylboranes. Structure of [NMe3Ph][C5H5BMe] , 1995 .