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
Dimerization of Molecular PhosphorusOxides.-The colorless compound P 8 O 12 ·2BH 3 (II) is characterized by 31 P-MAS NMR spectroscopy and mass spectrometry. As revealed by single crystal XRD, (II) crystallizes in the orthorhombic space group Pbca with Z = 8. Its principal building block is a novel P 8 O 12 framework, which originates from the fusion of two P 4 O 6 cages after cleavage of one P-O bond in each cage. -(TELLENBACH, AKBAR; JANSEN, MARTIN; Angew. Chem., Int. Ed. 40 (2001) 24, 4691-4694; MPI Festkoerperforsch., D-70569 Stuttgart, Germany; EN)
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.