Cp^*Ru(acac)—A Coordinatively Unsaturated, Stable 16‐Valence‐Electron Complex

Abstract

An unusually clear demonstration of the ease of addition of two‐electron donor ligands to the title complex 1 is provided by the molecular structure shown on the right. Complex 1 is readily accessible from [{Cp*RuOMe}2] and acetylacetone. The air‐sensitive, intensely red complex 1 adds CO and phosphane very rapidly and can be cleaved with cations such as Zn2⊕ and Mg2⊕ to give the very versatile Cp*Ru⊕ fragment.

Relative Binding Energies of Tertiary Phosphine Ligands to the Cp*RuOCH2CF3 (Cp* = η5-C5Me5) Moiety

“…8,9,18 The recent report by Caulton and co-workers of the [Cp*RuOR f ] 2 (OR f ) OCH 2 CF 3 ) (1) complex 9,19 affords an entryway into the thermochemistry of ligand binding to the Cp*RuOR f moiety by the rapid and quantitative nature of reaction 19, where the phosphine ligands initially used were sterically demanding ones (P i Pr 3 and PCy 3 ), analogous complex to those reported by Tilley 4 in the Cp*Ru(PR 3 )-Cl series. 8,9,18 The recent report by Caulton and co-workers of the [Cp*RuOR f ] 2 (OR f ) OCH 2 CF 3 ) (1) complex 9,19 affords an entryway into the thermochemistry of ligand binding to the Cp*RuOR f moiety by the rapid and quantitative nature of reaction 19, where the phosphine ligands initially used were sterically demanding ones (P i Pr 3 and PCy 3 ), analogous complex to those reported by Tilley 4 in the Cp*Ru(PR 3 )-Cl series.…”

Coordinatively Unsaturated Cp*Ru Alkoxo Complexes. 16.1Addition Products Cp*Ru(acac)L and Solution Equilibria1

“…The complex Cp*Ru(acac) ( 2 ) was first synthesized in the hope of generating a monomeric analogue to 1 but was later recognized to be a dimer in the solid state (Scheme ). The monomers are connected by a long (2.43 Å) bond between Ru and the central carbon of the acac ligand of a second Cp*Ru(acac) fragment, in the same way as has been found previously for [Cp*Rh(acac)] 2 2+ …”

Structure and Reactivity of Coordinatively Unsaturated Half‐Sandwich Iron, Ruthenium and Osmium Complexes

“…[49] A packing diagram showed a 18-electron dimeric structure consisting of two independent molecules in the asymmetric unit, linked through an inversion centre, and each ruthenium bonded to the γ-carbon of the symmetry related acac group ( Figure 5). [50] Despite this, there is numerous spectral evidence in support of the coordinatively unsaturated nature of [Cp*Ru-(acac)] in solution.…”