Protonierung des 1,1,3,3,5,5‐Hexakis(dimethylamino)λ5‐[1,3,5]triphosphinins. Cyclotrimethylentriphosphinsäure. NMR‐Daten,Kristallstrukturen und quantenchemische Rechnungen |
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Authors: | Gernot Heckmann Ekaterina Gorbunowa‐Jonas Stefan Plank Rudolf Janoschek Matthias Westerhausen Ekkehard Fluck |
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Abstract: | Protonation of 1,1,3,3,5,5‐Hexakis(dimethylamino)‐λ5‐[1,3,5]triphosphinine. Cyclotrimethylenetriphosphinic Acid. NMR Data, Crystal Structures, and Quantum Chemical Calculations Preparation of 1,1,3,3,5,5‐hexakis(dimethylamino)‐1,2‐dihydro‐3λ5,5λ5‐[1,3,5]triphosphininium‐tetrafluoroborate ( 3 ) und 1,1,3,3,5,5‐hexakis(dimethylamino)‐λ5‐[1,3,5]triphosphinanetriium‐tris(tetrafluoroborate) ( 4 ) from 1,1,3,3,5,5‐hexakis(dimethylamino)‐1λ5,3λ5,5λ5‐triphosphinine 1 and HBF4 · O(C2H5)2 are described. The structures of 3 und 4 are elucidated by n. m. r. and X‐ray structural analyses. By hydrolysis of 4 with conc. hydrochloric acid 1,3,5‐trioxo‐1λ5,3λ5,5λ5‐[1,3,5]triphosphinane‐1,3,5‐triol (cyclotrimethylene‐triphosphinic acid) ( 8 ) is formed. Neutralisation with NaOH yields its sodium salt 9 . 8 and 9 are characterized by their n. m. r. spectra. Quantum chemical calculations have been investigated for the compounds 1 ′– 4 ′ and the trianion 9 . The systems 1 ′– 4 ′ are distinguished from 1 – 4 by the size of the ligands at phosphorus which is reduced from N(CH3)2 to NH2, respectively. The aims of the calculations are to elucidate hybridisations and molecular structures, Lewis or resonance structures, electronic charge distributions and NMR chemical shifts. |
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Keywords: | 1,1,3,3,5,5‐hexakis(dimethylamino)‐λ 5‐[1,3,5]triphosphinine λ 5‐[1,3,5]triphosphininium‐tetrafluoroborate λ 5‐[1,3,5]triphosphinanetriium‐tris(tetrafluoroborate) 1,3,5‐trioxo‐λ 5‐[1,3,5]triphosphinane‐1,3,5‐triol cyclotrimethylenetriphosphinic acid NMR spectroscopy Crystal structure Quantum chemical calculations |
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