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P 8 O 12 ·2BH 3 − The Borane Adduct of a New Molecular Phosphorus Oxide
Author(s) -
Tellenbach Akbar,
Jansen Martin
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300217
Subject(s) - chemistry , adduct , raman spectroscopy , toluene , reactivity (psychology) , crystallography , borane , nuclear magnetic resonance spectroscopy , stoichiometry , spectroscopy , medicinal chemistry , stereochemistry , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics , optics
P 4 O 6 ·BH 3 , which readily forms from P 4 O 6 and Me 2 S·BH 3 in a stoichiometric reaction, dimerizes spontaneously at −30 °C in a concentrated toluene solution resulting in the crystallization of P 8 O 12 ·2BH 3 ( 1 ). The synthesis of 1 represents the first selective interconnection of molecular phosphorus chalcogenides leading to the formation of a new, flexible P 8 O 12 cage. The thermodynamic driving force for the dimerization reaction results from a gain of enthalpy due to enhanced P−O double‐bond contributions and a relief of angular strain. In terms of kinetics, the behavior of P 4 O 6 ·BH 3 , differing from that of other P 4 O 6 derivatives, is caused by the low π‐donor ability of BH 3 provoking a Michaelis−Arbuzov‐like reactivity at the adjacent phosphorus atom and thus inducing cage opening. 1 was characterized by means of X‐ray diffractometry (powder, single crystal), NMR spectroscopy (solution, solid), IR spectroscopy, Raman spectroscopy, and mass spectrometry. Mass spectrometric investigations suggest considerable BH 3 abstraction as well as an enhanced stability of P 8 O 12 ·BH 3 and P 8 O 12 , compared to 1 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)