Bimetallic rare-earth/platinum complexes ligated by phosphinoamides

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Coordination Chemistry

Background:

• Early-late heterometallic complexes featuring lanthanide and platinum are of interest for their unique electronic and structural properties.
• Phosphinoamide ligands offer versatile coordination modes, enabling the stabilization of unusual metal centers and oxidation states.

Purpose of the Study:

• To synthesize and characterize novel heterometallic early-late 5d/4f binuclear phosphinoamido lanthanide/platinum(0) complexes.
• To investigate the reactivity and stability of these complexes in solution.

Main Methods:

• Synthesis of heterometallic complexes via reaction of lanthanide complexes with a platinum(0) precursor in the presence/absence of LiCl.
• Characterization of the resulting complexes using spectroscopic and analytical techniques.
• Investigation of solution stability and decomposition pathways.

Main Results:

• Two types of heterometallic Ln/Pt(0) complexes, [(Ph2PNHPh)Pt{μ-(Ph2PNPh)}3Ln(μ-Cl)Li(THF)3] and [(Ph2PNHPh)Pt{μ-(Ph2PNPh)}3Ln{η(2)-(Ph2PNPh)}][Li(THF)4], were successfully synthesized for Ln = Y, Lu.
• Both synthesized complexes demonstrated instability in solution.
• The platinum(0) complex [Pt(Ph2PNHPh)4] was identified as a decomposition product.

Conclusions:

• The successful synthesis of novel heterometallic 5d/4f binuclear phosphinoamido complexes is reported.
• The observed decomposition highlights the challenges in stabilizing such highly reactive species in solution.
• The formation of [Pt(Ph2PNHPh)4] provides insight into the decomposition mechanism of these lanthanide/platinum(0) systems.