THE ISOLATION FROM DIETHYL-ETHER OF IONIC [(ME(2)N)(3)PI]I AND [(CH2=CHCH2)(2)PHPI]I, AND THE CRYSTALLOGRAPHICALLY CHARACTERIZED MOLECULAR SPOKE STRUCTURE PHME(2)PI(2)

Ten new compounds of stoichiometry R(3)PI(2) [R(3) = (o-MeOC(6)H(4))(3 ), (o-MeOC(6)H(4))(2)Ph, (o-MeOC(6)H(4))Ph(2), (p-FC6H4)(2)Ph, (p-FC6H 4)Ph(2), (p-CH2=CHC6H4)Ph(2). (CH2=CHCH2)(2)Ph (C6H11)Ph(2), (PhCH(2)C H(2))(3) or (Me(2)N)(3)] have been prepared by the direct reaction of PR(3) and I-2 in diethyl ether solution. The compounds have been chara cterised by Raman and solid-state P-31-{(H} magic angle spinning (MAS) and solution; NMR spectroscopy. Solid-state P-31-{H} MAS NMR studies indicate that the predominant solid-state species is the molecular 'sp oke' structure R(3)P-I-I; however, in some cases a minor peak was also assignable to the ionic species, [R(3)PI]I. Additionally, solid-state P-31-{H} MAS NMR studies of (Me(2)N)(3)PI2 and (CH(?)2=CHCH2)(2)PhPI( 2) indicate that. in contrast to all other compounds of stoichiometry R(3)PI(2) prepared in diethyl ether, they are exclusively ionic, [R(3) PI]I. The crystal structure of PhMe(2)PI(2) shows it to have the molec ular 'spoke' geometry, PhMe(2)P-I-I. d(I-I) = 3.408 Angstrom, previous ly observed for Ph(3)PI(2), in agreement with solid-state P-31-{H} MAS NMR results.