Silylated Sulfuric Acid: Preparation of a Tris(trimethylsilyl)oxosulfonium [(Me3 Si-O)3 SO]+ Salt.

The chemistry of silylated sulfuric acid, O2 S(OSiMe3 )2 (T2 SO4 , T=Me3 Si; also known as bis(trimethylsilyl) sulfate), has been studied in detail with the aim of synthesizing the formal autosilylation products of silylated sulfuric acid, [T3 SO4 ]+ and [TSO4 ]- , in analogy to the known protonated species, [H3 SO4 ]+ and [HSO4 ]- . The synthesis of the [TSO4 ]- ion only succeeds when a base, such as OPMe3 that forms a weakly coordinating cation upon silylation, is reacted with T2 SO4 , resulting in the formation of [Me3 POT]+ [TSO4 ]- . [T3 SO4 ]+ salts could be isolated starting from T2 SO4 in the reaction with [T-H-T]+ [B(C6 F5 )4 ]- or T+ [CHB11 Br6 H5 ]- when a weakly coordinating anion is used as counterion. All silylated compounds could be crystallized and structurally characterized.

On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions.

Attempts have been made to prepare salts with the labile tris(trimethylsilyl)chalconium ions, [(Me3 Si)3 E]+ (E=O, S), by reacting [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ] and Me3 Si[CB] (CB- =carborate=[CHB11 H5 Cl6 ]- , [CHB11 Cl11 ]- ) with Me3 Si-E-SiMe3 . In the reaction of Me3 Si-O-SiMe3 with [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ], a ligand exchange was observed in the [Me3 Si-H-SiMe3 ]+ cation leading to the surprising formation of the persilylated [(Me3 Si)2 (Me2 (H)Si)O]+ oxonium ion in a formal [Me2 (H)Si]+ instead of the desired [Me3 Si]+ transfer reaction. In contrast, the expected homoleptic persilylated [(Me3 Si)3 S]+ ion was formed and isolated as [B(C6 F5 )4 ]- and [CB]- salt, when Me3 Si-S-SiMe3 was treated with either [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ] or Me3 Si[CB]. However, the addition of Me3 Si[CB] to Me3 Si-O-SiMe3 unexpectedly led to the release of Me4 Si with simultaneous formation of a cyclic dioxonium dication of the type [Me3 Si-µO-SiMe2 ]2 [CB]2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamics of the [(Me3 Si)3 E]+ and [(Me3 Si)2 (Me2 (H)Si)E]+ ion formation are presented as well as mechanistic investigations on the template-driven transformation of the [(Me3 Si)3 E]+ ion into a cyclic dichalconium dication [Me3 Si-µE-SiMe2 ]2 2+ .

Borane Adducts of Hydrazoic Acid and Organic Azides: Intermediates for the Formation of Aminoboranes.

The reaction of HN3 with the strong Lewis acid B(C6 F5 )3 led to the formation of a very labile HN3 ⋅B(C6 F5 )3 adduct, which decomposed to an aminoborane, H(C6 F5 )NB(C6 F5 )2 , above -20 °C with release of molecular nitrogen and simultaneous migration of a C6 F5 group from boron to the nitrogen atom. The intermediary formation of azide-borane adducts with B(C6 F5 )3 was also demonstrated for a series of organic azides, RN3 (R=Me3 Si, Ph, 3,5-(CF3 )2 C6 H3 ), which also underwent Staudinger-like decomposition along with C6 F5 group migration. In accord with experiment, computations revealed rather small barriers towards nitrogen release for these highly labile azide adducts for all organic substituents except R=Me3 Si (m.p. 120 °C, Tdec =189 °C). Hydrolysis of the aminoboranes provided C6 F5 -substituted amines, HN(R)(C6 F5 ), in good yields.

Synthesis and Characterization of Silylated Phosphonium [P(OSiMe3)4]+ and Phosphate [O2P(OSiMe3)2]- Salts.

Starting from an optimized synthesis of silylated phosphoric acid, OP(OSiMe3)3, a borate salt bearing the [P(OSiMe3)4]+ cation was generated in the reaction of OP(OSiMe3)3 with [Me3Si-H-SiMe3][B(C6F5)4], isolated, and fully characterized. Analogously to the protonated species, phosphoric acid (H3PO4) reaction of OP(OSiMe3)3 with a base led to the formation of the unknown [O2P(OSiMe3)2]- anion, which could be crystallized as potassium salt and structurally characterized, too. Both [P(OSiMe3)4]+ and [O2P(OSiMe3)2]- can be regarded as the formal autoprotolysis products of OP(OSiMe3)3.

A Dimer of Hydrogen Cyanide Stabilized by a Lewis Acid.

A highly labile dimer of hydrogen cyanide, HCN⋅⋅⋅HCN, was extracted from liquid HCN by adduct formation with the bulky Lewis acid B(C6 F5 )3 , affording HCN⋅⋅⋅HCN-B(C6 F5 )3 , which was fully characterized. The influence of the solvent (HCN, CH2 Cl2 , and aromatic hydrocarbons) on the crystallization process was studied, revealing dimer formation when using HCN or CH2 Cl2 as solvent, whereas aromatic hydrocarbons led to the formation of monomeric arene⋅⋅HCN-B(C6 F5 )3 adducts, additionally stabilized by η6 -coordination of the aromatic ring system similar to well-known half-sandwich complexes.

HPCO-A Phosphorus-Containing Analogue of Isocyanic Acid.

We describe the isolation and spectroscopic characterization of the heavier phosphorus-containing analogue of isocyanic acid (HPCO), and its isotopologue (DPCO). This fundamental small molecule, which has been postulated to exist in interstellar space, has thus far only been observed at low gas phase concentrations or in inert gas matrices. In this report we describe its synthesis, spectroscopic properties, and reactivity in solution.

Isolation of Labile Pseudohalogen NSO Species.

A new synthetic approach enabled the generation of highly labile thionylimide, H-NSO, which was trapped by adduct formation with the bulky Lewis acid B(C6 F5 )3 and fully characterized. For comparison, a series of different Me3 Si-NSO Lewis acid adducts were studied. Treatment of Me3 Si-NSO with the silylium ion [Me3 Si](+) led to the formation of the hitherto unknown iminosulfonium ion [Me3 Si-N=S-O-SiMe3 ](+) , which could be isolated and fully characterized as a salt in the presence of weakly coordinating carborate anions.