Synthesis, characterization, computational studies, and reactivity of platinum(II) complexes of alkyl phosphite ligands.

• The crystal structures of several Pt(P(OR) 3) 2 X 2 were obtained and compared with spectral data. • Michaelis-Arbuzov-type dealkylation during synthesis was observed for some of the phosphite ligands. • Computational studies were used to understand the electronic structure of phosphite ligands. Air-stable phosphite-ligated platinum complexes of the form cis -Pt(P(OR) 3) 2 Cl 2 and cis -Pt(P(OR) 3) 2 Me 2 based on five small alkyl phosphite ligands have been synthesized and characterized. The crystal structures for several of these species are reported, allowing for comparison between spectroscopic and structural parameters. Michaelis-Arbuzov-type dealkylation during synthesis was observed for some of the phosphite ligands, and a dealkylated product was structurally characterized. Density Functional Theory (DFT) and Quantum Theory of Atoms in Molecules (QTAIM) was also used to examine the electronic structure of the phosphite compounds. The QTAIM results support the increased π-acidity of the phosphite ligands compared to analogous phosphines. Thermolysis experiments were performed to examine the stability and reactivity of Pt(P(OR) 3) 2 X 2 species. It was found that coordinated P(OiPr) 3 ligands decompose via cyclometallation and propylene extrusion. Air- stable phosphite-ligated platinum complexes of the form cis -Pt(P(OR) 3) 2 Cl 2 and cis -Pt(P(OR) 3) 2 Me 2 based on five small alkyl phosphite ligands have been synthesized and characterized. The crystal structures for several of these species are reported, allowing for comparison between spectroscopic and structural parameters. Michaelis-Arbuzov-type dealkylation during synthesis was observed for some of the phosphite ligands, and a dealkylated product was structurally characterized. Density Functional Theory (DFT) and Quantum Therory of Atoms in Molecules (QTAIM) was also used to examine the electronic structure of the phosphite compounds. [Display omitted] [ABSTRACT FROM AUTHOR]