Syntheses, Reactivity, and X‐ray Structure Analyses of the Dimeric Pentaphosphides [(<i>t</i>Bu₃Si)₃P₅M₂]₂ (M = Na, Ag) and the Bicyclo[2.1.0]pentaphosphane (<i>t</i>Bu₃Si)₃P₅

Abstract

Abstract The sodium pentaphosphide dimer [( t Bu 3 Si) 3 P 5 Na 2 (THF)] 2 has been synthesized in high yield from the reaction of four equivalents of the sodium silanide t Bu 3 SiNa with P 4 . X‐ray quality crystals of the sodium pentaphosphide dimer [( t Bu 3 Si) 3 P 5 Na 2 (THF)] 2 (monoclinic, P 2 1 / n ) were grown from benzene. The sodium pentaphosphide ( t Bu 3 Si) 3 P 5 Na 2 can be oxidized with one equivalent of TCNE to give the bicyclo[2.1.0]pentaphosphane ( t Bu 3 Si) 3 P 5 ; it also reacts with AgOCN to give the silver pentaphosphide [( t Bu 3 Si) 3 P 5 Ag 2 ] 2 (monoclinic, P 2 1 / n ). Crystals of the pentaphosphane ( t Bu 3 Si) 3 P 5 (monoclinic, P 2 1 / c ) suitable for X‐ray diffraction were obtained from hexane at –25 °C. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2005)