Transfer of polyantimony units.

Area of Science:

• Organometallic Chemistry
• Main Group Chemistry
• Coordination Chemistry

Background:

• Transfer reagents are crucial for synthesizing metastable compounds in chemistry.
• The development of novel reagents facilitates access to unique molecular architectures and bonding.

Purpose of the Study:

• To synthesize and characterize a novel polyantimony triple decker complex using a transfer reagent approach.
• To explore the utility of this complex as a transfer reagent for novel antimony ligand complexes.
• To investigate the structural diversity and bonding of resulting transition metal-antimony complexes.

Main Methods:

• Synthesis of the novel polyantimony triple decker complex [(Cp''Zr)2(μ,η1:1:1:1:1:1-Sb6)] from [Cp''2ZrCl2] and KSb(SiMe3)2.
• Reactions of the synthesized complex with various CpR-substituted transition metal halides (Ni, Co, Fe).
• Characterization of the resulting antimony ligand complexes using spectroscopic and crystallographic methods.
• Density Functional Theory (DFT) calculations to elucidate bonding.

Main Results:

• Formation of the novel chair-like Sb66- ligand within the triple decker complex [(Cp''Zr)2(μ,η1:1:1:1:1:1-Sb6)] (1).
• Successful transfer of antimony units (Sb1 and Sb6) to form diverse transition metal complexes, including cubane-like and trigonal bipyramidal structures.
• Synthesis of novel complexes such as [(Cp'''Ni)4(μ3-Sb)4] (2), [(Cp'''Co)4(μ3-Sb4)] (3a), [(CpBnCo)3(μ3-Sb)2] (4), [(Cp'''Fe)3(μ3-Sb)2] (5), and [(Cp'''Fe)3(μ3,η4:4:4-Sb6)] (6).
• DFT calculations provided insights into the electronic structure and bonding of the synthesized compounds.

Conclusions:

• The novel polyantimony triple decker complex is an effective transfer reagent for antimony.
• This methodology allows for the construction of unique antimony-containing transition metal complexes with varied geometries.
• The study expands the scope of antimony ligand chemistry and provides a new route to complex antimony architectures.