T-Shaped Palladium and Platinum {MNO}¹⁰ Nitrosyl Complexes

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Inorganic Chemistry

Background:

• Nitrosyl complexes are crucial in catalysis and materials science.
• Understanding metal-nitrosyl bonding is key to controlling reactivity.
• Steric effects significantly influence coordination geometries in metal complexes.

Purpose of the Study:

• To synthesize and characterize a series of T-shaped nitrosyl complexes.
• To investigate the factors governing the bent metal-nitrosyl coordination mode.
• To elucidate the electronic structure and bonding in these complexes.

Main Methods:

• Synthesis of [M(PR3)2(NO)]+ complexes (M = Pd, Pt; R = tBu, Ad).
• Characterization using X-ray crystallography and 15N NMR spectroscopy.
• Computational analysis using DFT-based energy decomposition.

Main Results:

• Successfully synthesized and characterized a homologous series of T-shaped nitrosyl complexes.
• Observed distinctly bent M-NO angles (~123°) in the solid state.
• DFT calculations revealed steric repulsion prevents linear nitrosyl coordination despite electronic preference.

Conclusions:

• The steric bulk of phosphine ligands dictates the bent nitrosyl coordination geometry.
• This study provides insights into controlling coordination modes in organometallic complexes.
• The findings contribute to the fundamental understanding of metal-nitrosyl interactions.