NHC-stabilized Parent Arsanylalanes and -gallanes

Area of Science:

• Main group chemistry
• Organometallic compounds
• Inorganic synthesis

Background:

• Exploration of low-coordinate main group elements is crucial for understanding bonding and reactivity.
• Stabilization of reactive main group species often requires bulky ligands or Lewis base adducts.
• Arsanylalanes and arsanylgallanes represent underexplored areas in main group chemistry.

Purpose of the Study:

• To synthesize and characterize unprecedented monomeric, Lewis base-stabilized arsanylalane and arsanylgallane compounds.
• To investigate different synthetic routes, including salt metathesis and H2-elimination pathways.
• To explore the synthesis of organo-substituted and branched derivatives.

Main Methods:

• Synthesis of IDipp⋅E'H2AsH2 (E'=Al, Ga) via salt metathesis of KAsH2 with IDipp⋅E'H2Cl.
• Investigation of H2-elimination from AsH3 and IDipp⋅E'H3 (E'=Al, Ga).
• Synthesis of organo-substituted IDipp⋅GaH2AsPh2 and IDipp⋅AlH2AsPh2 via reaction of KAsPh2.
• Synthesis of branched IDipp⋅E'H(EH2)2 (E'=Al, Ga; E=P, As) via salt metathesis.
• Density Functional Theory (DFT) computations to analyze reaction pathways and product stability.

Main Results:

• Successful synthesis and characterization of unprecedented monomeric arsanylalane and arsanylgallane compounds stabilized by a Lewis base (IDipp).
• Salt metathesis proved more advantageous than the H2-elimination pathway for synthesizing parent compounds.
• Synthesis of novel organo-substituted and branched arsanylalane and arsanylgallane derivatives.
• DFT calculations provided insights into the mechanistic aspects and stability of the synthesized compounds.

Conclusions:

• The study establishes new synthetic routes to Lewis base-stabilized arsanylalanes and arsanylgallanes.
• The reported compounds represent the first monomeric, parent examples of these classes.
• DFT computations support the experimental findings and offer a deeper understanding of the reaction mechanisms.