Abstract
AbstractP4O6·BH3, which readily forms from P4O6 and Me2S·BH3 in a stoichiometric reaction, dimerizes spontaneously at −30 °C in a concentrated toluene solution resulting in the crystallization of P8O12·2BH3 (1). The synthesis of 1 represents the first selective interconnection of molecular phosphorus chalcogenides leading to the formation of a new, flexible P8O12 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 P4O6·BH3, differing from that of other P4O6 derivatives, is caused by the low π‐donor ability of BH3 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 BH3 abstraction as well as an enhanced stability of P8O12·BH3 and P8O12, compared to 1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
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