Synthesis of Metallostannylenes from Transition Metal Polyhydride Complexes

Area of Science:

• Organometallic Chemistry
• Main Group Chemistry
• Coordination Chemistry

Background:

• Transition metal polyhydride complexes are versatile precursors in inorganic synthesis.
• Amidostannylenes are reactive main group compounds with ambiphilic character.
• Understanding the reactivity of amidostannylenes with transition metals is crucial for developing new synthetic methodologies.

Purpose of the Study:

• To synthesize high-valent open-chain metallostannylene hydride complexes.
• To investigate the reaction pathways between transition metal polyhydrides and aryl-substituted amidostannylenes.
• To explore the role of amidostannylene ambiphilicity in metal-main group bond formation.

Main Methods:

• Reaction of iridium polyhydride complexes with various amidostannylenes.
• Characterization of novel metallostannylene and amidostannylene complexes using spectroscopic techniques.
• Analysis of reaction byproducts and mechanistic pathways.

Main Results:

• Synthesis of metallostannylenes (^MeBDI^Dipp)IrH₃SnDMP (1) and Cp*IrH₃SnDMP (2).
• Formation of bis(metallostannylene) Cp*IrH₂(SnDMP)₂ (3) via reaction with a second amidostannylene equivalent.
• Synthesis of new amidostannylenes DMPSn[N(Dipp)(SiMe₃)] (4) and TripSn[N(Dipp)(SiMe₃)] (5).
• Observation of competing pathways including stannylene coordination and H₂ release in the reaction of (^MeBDI^Dipp)IrH₄ with amidostannylene 5, yielding complex 6.
• Metallostannylene formation characterized as formal deprotonation of the transition metal polyhydride by the amidostannylene.

Conclusions:

• Amidostannylenes efficiently react with transition metal polyhydrides to form high-valent metallostannylenes.
• The ambiphilicity of amidostannylenes is key for successful Ir-Sn bond formation.
• Reaction pathways can be tuned, leading to either metallostannylene formation or stannylene coordination.