A reactive Ru-binaphtholate building block with self-tuning hapticity.

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Ruthenium Complexes

Background:

• Ruthenium complexes are vital in catalysis and materials science.
• Atropisomeric ligands like binaphtholates offer unique stereochemical control.
• Exploring novel ligand coordination modes enhances synthetic versatility.

Purpose of the Study:

• To introduce a versatile ruthenium-binaphtholate (BINO) building block.
• To investigate new coordination modes of the BINO ligand with ruthenium.
• To demonstrate the synthetic utility of the BINO complex for generating diverse ruthenium derivatives.

Main Methods:

• Synthesis of a novel ruthenium-binaphtholate complex (7) from RuCl(2)(PPh(3))(3) and Tl(2)((S)-BINO).
• Characterization of isomers 7' and 7″ using spectroscopic techniques and single-crystal X-ray diffraction.
• Exploration of the reactivity of complex 7 to form new derivatives under mild conditions.

Main Results:

• A versatile Ru-BINO building block (7) was successfully synthesized.
• Novel η(3)-CCO,η(3)-O'C'C' bis(enolate) BINO bonding mode was observed, highlighting ligand flexibility.
• Complex 7 and its derivatives demonstrated stability with two to four additional ligands, enabling facile transformations into acetonitrile, pyridine, and vinylidene complexes.

Conclusions:

• The reported Ru-BINO complex provides a facile entry into atropisomeric binaphtholate ruthenium chemistry.
• The observed diverse coordination modes and stabilization of multiple ligands underscore the BINO moiety's flexibility.
• The study proposes (13)C{(1)H} NMR signatures for various BINO coordination modes, aiding future research in late-metal BINO chemistry.