title: New synthetic procedures to catena-phosphorus cations: preparation and dissociation of the first cyclo-phosphino-halophosphonium salts.
abstract: Chlorination of 1,2,3,4-tetracyclohexyl-cyclo-tetraphosphine (2) by PhICl(2) or PCl(5) in the presence of Me(3)SiOTf or GaCl(3) provides a stepwise approach to salts of the first cyclo-phosphino-chlorophosphonium cations [Cy(4)P(4)Cl](+) ([19](+)) and [Cy(4)P(4)Cl(2)](2+) ([20](2+)). The analogous iodo derivative [Cy(4)P(4)I](+) ([17](+)) is obtained as the tetraiodogallate salt from reaction of 2 with I(2) in the presence of GaI(3). Reactions of the dication [20](2+) with PMe(3) or dmpe effect a dissociation of the cyclic framework resulting in the formation of salts containing [Me(3)PPCyPCyPMe(3)](2+) ([27](2+)), [dmpeCyP](2+) ([29](2+)), and [dmpeCyPCyP](2+) ([30](2+)), respectively. The new cations represent phosphine complexes of the [PCy](2+) and [P(2)Cy(2)](2+) cationic fragments from [20](2+), demonstrating the coordinate nature of the phosphinophosphonium bonds in cyclo-phosphino-halophosphonium cations. The compounds have been characterized by NMR spectroscopy, single crystal X-ray crystallography, and Raman spectroscopy.
authors.affiliation: Department of Inorganic and Analytical Chemistry, Westfälische Wilhelms-University Münster, Germany. jweigand@uni-muenster.de
authors.forename: Jan J
authors.initials: JJ
authors.lastname: Weigand
authors.forename: Neil
authors.initials: N
authors.lastname: Burford
authors.forename: Reagan J
authors.initials: RJ
authors.lastname: Davidson
authors.forename: T Stanley
authors.initials: TS
authors.lastname: Cameron
authors.forename: Patrick
authors.initials: P
authors.lastname: Seelheim