Carbonylation of benzyne at polynuclear ruthenium centres

Abstract

Carbonylation (1 atm, 25 °C) of [Ru₃(CO)₇(µ-PPh₂)₂(µ₃-C₆H₄)] gives [Ru₃(CO)₈(µ-PPh₂)₂(µ₃-C₆H₄CO)], arising from linking of µ₃-benzyne with one molecule of CO, while [Ru₄(CO)₁₁(µ₄-PPh)(µ₄-C₆H₄)] and [Ru₅(CO)₁₃(µ₄-PPh)(µ₅-C₆H₄)] react with CO (50 atm, 60–100 °C) to afford [Ru₃(CO)₁₀(µ₃-PPh){µ-C₆H₄(CO)₂}] and/or [Ru₂(CO)₇(µ-P(Ph)C(O)C₆H₄)], involving linking of µ₄- and µ₅-benzyne with one or two CO molecules; the structures of the products have been established by X-ray diffraction.