Beiträge zur Chemie des Phosphors, 135 [1]. Synthese und Strukturen neuer polycyclischer Organophosphane PnRm (m < n) / Contributions to the Chemistry of Phosphorus, 135 [1]. Synthesis and Structures of Novel Polycyclic Organophosphanes PnRm (m < n)

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Abstract
The novel polycyclic organophosphanes b-P9R5, P10R6, P10R4, P11R5, and P13R5 (R = Me, Et, i-Pr) have been obtained by reacting RPCl2 with white phosphorus and magnesium or by thermolysing P7R5 (perhaps in the presence of P8R6, P9R5 or (PR)5). A strategy for the enrichment or isolation of polycyclic organophosphanes PnRm (m < n) from complex reaction mixtures is described. The structures of the above mentioned compounds have been unambiguously clarified by 31P NMR spectroscopy or X-ray structure analysis. The results clearly indicate that the corresponding phosphorus hydrides PnNm have the same structures. The general structural principles of polycyclic phosphanes are dicussed.