Reaction of C(PPh3)2 with MI2 Compounds (M = Zn, Cd) - Formation and Crystal Structures of [I2Zn{C(PPh3)2}], [(I2Cd{C(PPh3)2})2] and the Salt-Like Compounds (HC{PPh3}2)[MI3(THF)] and (HC{PPh3}2)2[ZnI4]

The reaction of the carbodiphosphorane C(PPh3)(2) (1) with group 12 MI2 compounds in THF leads to the salts (HC{PPh3}(2))[MI3(THF)] (M = Zn2+, 2; Cd2+, 3) in good yields upon proton abstraction from the solvent. The salt-like complex (HC{PPh3}(2))(2)[ZnI4] (4) formed upon reaction of ZnI2 with 1 in toluene and subsequent heating of the resulting powder in 2-bromofluorobenzene. When this reaction was carried out in 2-bromofluorobenzene as the solvent, no proton transfer occurred, and the colorless addition compounds [I2Zn <- 1] (5) and [I2Cd <- 1](2) (6) were isolated. Compound 5 is monomeric, whereas in 6 the monomeric units are linked by bridging iodine ligands to produce a dimer. All compounds were characterized by X-ray analyses and P-31 NMR and IR spectroscopy.