Thorsten Berends

Neuartige elementorganische Sauerstoffsäuren des Phosphors und Schwefels [1]†

Die neuartige Imidazoliophosphonsaure Im—PO3H (7, Im = 2-{1, 3-diisopropyl-4, 5-dimethylimidazolio}) wird durch Hydrolyse des Phosphonylchlorids [Im-P(O)Cl2]Cl (6), das durch direkte Umsetzung des stabilen 2, 3-dihydro-1, 3-diisopropyl-4, 5-dimethylimidazol-2-ylidens (5) mit P(O)Cl3 zuganglich ist, erhalten. Die neuartige kationische Sulfonsaure [Im—SO3H]X ist als BF4- bzw. SbF6-Salz (11a, b) durch Umsetzung des Betains Im—SO3 (10) mit HBF4· Et2O bzw. HF/SbF5 zuganglich. Die Kristallstrukturen von 7 und 11b werden ermittelt und diskutiert. Novel Elementorganic Oxo-Acids of Phosphorus and Sulfur [1] The novel imidazoliophosphonate acid Im—PO3H (7, Im = 2-{1, 3-diisopropyl-4, 5-dimethylimidazolio}) is prepared through hydrolysis of the phosphonyl chloride [Im—P(O)Cl2]Cl (6) formed by the direct reaction of the stable 2, 3-dihydro-1, 3-diisopropyl-4, 5-dimethylimidazol-2-ylidene (5) with P(O)Cl3. The novel cat ionic sulfonic acid [Im—SO3H]X (11) is formed as its BF4 (11a) and SbF6 (11b) salt on treatment of the betaine Im—SO3 (10) with HBF4· Et2O or HF/SbF5. The crystal structures of 7 and 11b are reported and discussed.

The 2,8-dioxa-5-aza-1-sila-bicyclo[3.3.01.5]octane PhN(CH2CH2O)2SiH2 as reducing reagent: synthesis and molecular structure of PhN(CH2CH2O)2Sn

Abstract The synthesis of the 2,8-dioxa-5-aza-1-stanna-bicyclo[3.3.01.5]octane [PhN(CH2CH2O)2Sn]n (3) by a combined ligand exchange/redox reaction and independently by the reaction of tin(II)butoxide with N-phenyldiethanolamine is reported. Compound 3 was characterized by elemental analysis and single crystal X-ray diffraction analysis. In the solid state, it is a coordination polymer via intermolecular O→Sn interactions at O-Sn distances of 2.325 (3) and 2.379 (3) Å. The intramolecular N→Sn interactions at distances of 2.818 (3) and 3.096 (3) Å are rather weak.

Bis{deca­carbonyl­bis­[μ-2,2′-(phenyl­imino)­diethano­lato]ditin(II)ditungsten(0)(2 Sn—W)} hexa­carbonyl­tungsten(0)

In the title 2:1 adduct, [Sn2W2(C10H13NO2)2(CO)10]2[W(CO)6], the complete hexacarbonyltungsten molecule is generated by a crystallographic inversion centre. The heterometallic molecule features a central Sn2O2 core with essentially equal Sn—Oethoxy bond lengths. The second ethoxy O and amine N atoms of each N,O,O′-tridentate ligand coordinate to one Sn atom only. The NO3 donor atoms occupy basal positions and the W atom the apical position in a distorted square-pyramidal geometry for each Sn atom. The W atoms are approximately syn to each other but the central metal core is non-planar [W—Sn⋯Sn—W pseudo-torsion angle = 43.573 (16)°]. One of the carbonyl ligands in the heterometallic molecule is disordered over two orientations with equal occupancies. In the crystal, the heterometallic molecules associate via C—H⋯O interactions, forming supramolecular layers with undulating topology in the ab plane. These stack along the c axis, defining voids which are occupied by the W(CO)6 molecules.

Collidinium- und Imidazolium-Salze Fluor-haltiger Anionen. Die Kristallstruktur von [CollH]2 [AsF6][As2 F11] (Coll = 2,4,6-Trimethylpyridin) / Collidinium and Imidazolium Salts of Fluorine-Containing Anions. The Crystal Structure of [CollH]2[AsF6][As2F11] (Coll = 2,4,6-Trimethylpyridine)

Abstract Die Kristall struktur von [CollH]2 [AsF6][As2F11] (Coll = 2,4,6-Trimethylpyridin) Collidinium and Imidazolium Salts of Fluorine-Containing Anions. The Crystal Structure of [CollH]2[AsF6][As2F11] (Coll = 2,4,6-Trimethylpyridine) From s-Collidine (1, Coll) and aqueous HF compounds of the composition Coll · n HF (n = 1 -2) are formed which are transformed to [CollH]+ [HF2]- (2) by sublimation. [CollH]2[AsF6][As2F] J (3) is obtained from 1 and the superacid system HF/AsF5. 2 reacts with 2,3-dihydro-l,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (4, Im) to give the imidazo lium salt [ImH]+ [HF2]- (5). Hydrogen bonds in the crystal structure of [CollH]2[AsF6][As2Fn ] (3) are discussed.