Study of metal scrambling in the trinuclear {Pt₂Se₂M} (M = Pt, Pd, Au) system using an electrospray mass spectrometry (ESMS) directed synthetic methodology; isolation and crystallographic characterization of {Pt₂(µ₃-Se)₂(PPh₃)₄[Pt(cod)]}{PF₆}₂ and {Pt(μ₃-Se)₂(PPh₃)₂[Pt(cod)]₂}{PF₆}₂ (cod = Cyclo-octa-1,5-diene)

Abstract

Pt₂(μ-Se)₂(PPh₃)₄ reacts with PtCl₂(cod) to give {Pt₂(μ₃-Se)₂(PPh₃)₄[Pt(cod)]}²⁺ and an unexpected cod-rich product that arises from metal scrambling, viz. {Pt(μ₃-Se)₂(PPh₃)₂[Pt(cod)]₂}²⁺. The formation of these species was detected and followed by electrospray mass spectrometry (ESMS) and subsequently verified by batch synthesis and crystallographic characterization. Other metal-scrambled aggregate products were successfully detected.