[Ru₄(CO)₈(μ-OOCCH₂CH₃)₄(THF)₂] and [Ru₃(μ₃-OH)(CO)₆(μ-OOC^tBu)₄(OOC^tBu)]: Novel Multinuclear Ruthenium Carbonyl Carboxylates

Abstract

The reaction of Ru 3 (CO) 12 with pivalic or propionic acid leads to the formation of two novel multinuclear ruthenium complexes, [Ru 4 (CO) 8 (μ-OOCCH 2 CH 3 ) 4 (THF) 2 ] (1) and [Ru 3 (μ 3 -OH)(CO) 6 (μ-OOC t Bu) 4 (OOC t Bu)] (2). Compound 1 is among the few examples of discrete tetranuclear ruthenium compounds showcasing a "dimer of dimers" paddlewheel structure, in which two "Ru 2 (CO) 4 (μ-OOCCH 2 CH 3 ) 2 (THF)" fragments are linked via Ru−O interactions. Compound 2 features a unique structural motif in which a triangular Ru 3 core is connected via a μ 3 -OH ligand. Note pubs.acs.org/Organometallics

Synthesis, spectroscopic characterization and DFT study of dinuclear ruthenium sawhorse-type complexes derived from the reaction of trinuclear aggregates and (Z)-5-arylidenerhodanines

“…These authors found, through DFT calculations, that the formation of the tetranuclear ruthenium occurs by a nucleophilic attack involving the HOMO, localized mostly along the Ru(1)-Ru(2) bond, and the LUMO localized along the Ru(2)-Ru(3) bond. More recently, the tetranuclear ruthenium complex [Ru 2 (CO) 4 (µ-OOCR) 2 (THF) 2 ] 2 6c [29] linked via Ru-O bonds was derived from pivalic acid (R=(CH 3 ) 3 COOH) and is obtained after formation of the polymeric [Ru 2 (CO) 4 (µ-OOCR) 2 ] n 4e. Finally, similar to previous work, a theoretical investigation suggests nucleophilic attack during formation of the tetrameric compound.…”