ChemInform Abstract: Phosphoranide Ligands with Variable Coordination Modes. Synthesis, Properties, and X-Ray Crystal Structures of ((η2-HcyclenP)Pt(Cl)PPh3)BF4 and ((H2cyclenP)PtCl2PPh3)Cl.

ChemInform Abstract

Deprotonation of the cationic phosphoranide-Pt(II) complex (I) results in the formation of the neutral complex (II) in which the phosphoranide acts as a bidentate PN ligand. Treating (II) with HBF₄ leads to the monoprotonated derivative (III) in which one of the P-N bonds of the ligand unit is cleaved and the proton is attached to that N atom. (III) reacts with HCl to give the tetrafluoroborate analogue (IV) to (I), while treatment of (III) with NaCl in DMSO leads to (I) and (II) via disproportionation. The structures of (I) (space group Pcab, Z = 8) and (III) (P2₁/c, Z=4) are determined by X-ray analysis.