The Synthesis, Structure, and Chemistry of 10-Pn-3 systems: Tricoordinate Hypervalent Pnictogen Compounds

Article abstract of DOI:10.1021/ja00237a001

A set of previously unknown tricoordinate pnictogen compounds, 10-Pn-3 ADPnO, has been synthesized.The chemistry of these systems has been studied.Reactions with alcohols, α-dicarbonyl compounds, halogens, transition metals, protic acids, and acetylenes are among the chemistry described.In general, it was found that 10-As-3 ADAsO and 10-Sb-3 ADSbO systems behave similarly and offer different chemistry from that of the 10-P-3 ADPO system.Among these unusual reactions is a novel C-C bond forming reactions with hexafluoro-2-butyne.The electronic structure of these systems has been considered in light of preliminary ab initio molecular orbital calculations.The cyclic voltametry data on the 10-Pn-3 ADPnO system have been measured and are in accord with theoretical expectations.X-ray structures on a wide variety of derivatives provide insight into the chemistry of these systems.Phosphorus compounds with coordination numbers ranging from 2 to 6 have been characterized, and a trend is observed for 31P-15N coupling constants and phosphorus coordination number.