Facile insertion and halogen migration reactions of the hexaphosphapentaprismane cage (P6C4Bu4)-Bu-t with zerovalent and divalent platinum complexes

摘要

The hexaphosphapentaprismane (P6C4Bu4)-Bu-t undergoes specific insertion of the zerovalent platinum fragment [Pt(PPh3)(2)] into the unique P-P bond between the 5-membered rings to afford [Pt(PPh3)(2)(P6C4Bu4)-Bu-t]. A similar reaction with the Pt(II) complexes [{PtCl2(PMe3)}(2)] and [PtCl2(eta(4)-COD)] results in both insertion and chlorine migration reactions. The complexes [Pt(PPh3)(2)(P6C4Bu4)-Bu-t], trans[PtCl(PMe3)(P6C4Bu4Cl)-Bu-t], cis-, trans-[{PtCl2(PMe3)}mu-{P6C4t-Bu-4}{PtCl2(PMe3)}], [{(PtClP6C4Bu4Cl)-Bu-t}(2)] and cis-[PtClP6-C-4 (Bu4Cl)-Bu-t((P6C4Bu4)-Bu-t)] have been structurally characterized by single crystal X-ray diffraction and multinuclear NMR studies.