Cluster chemistry. 61. Addition of HX (XCl, Br,I) or AuCl(PPh₃) to an open Ru₅ cluster. X‐ray structures of Ru₅(μ‐H)(μ₅‐C₂PPh₂)(μ‐PPh₂)(μ‐Br)(CO)₁₃ and Ru₅(μ‐H)(μ₅‐C₂PPh₂)(μ₃‐I)(μ‐PPh₂)(CO)₁₂

Abstract

Abstract Reactions of aqueous HX (XCl, Br) or of AuCl(PPh 3 ) with Ru 5 (μ 5 ‐C 2 PPh 2 )(μ‐PPh 2 )(CO) 13 result in addition of the 4e‐donor set (H + X) or (Au(PPh 3 ) + Cl) with concomitant opening of two RuRu bonds to give complexes containing dimetallated triangular of ‘scorpion’ cores. Aqueous HI reacts similarly, but in this case the iodide ligand spans three Ru atoms, the (H + I) set acting as 6e‐donor. The structures of the two title compounds were confirmed by X‐ray crystallographic studies. Ru 5 (μ‐H)(μ 5 ‐C 2 PPh 2 )(μ‐PPh 2 )‐(μ‐Br)(CO) 13 is triclinic, space group P 1 , a = 9.689(2), b = 11.874(2), c = 20.005(4) Å, α = 84.66(2), β = 82.90(6), λ = 67.51(6)°, Z = 2; 6478 data with I > 2σ( I ) were refined to R = 0.0368, R w = 0.0362. Ru 5 (μ‐H)(μ 5 ‐C 2 PPh 2 )(μ 3 ‐I)(μ‐PPh 2 )‐(CO) 12 .CH 2 Cl 2 is monoclinic, space group P 2 1 / n , a = 14.809(4), b = 20.721(4), c = 17.698(5) Å, β = 111.42(2)°, Z = 4; 7815 data with I > 2σ( I ) were refined to R = 0.0440, R w = 0.0416.