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Updated: Jun 10, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis, Bonding, and Reduction Chemistry of LBeBrY Complexes (L = Lewis Base, Y = Ar, NR2)
Corinna Czernetzki1,2, Merle Arrowsmith1,2, Thomas Kroll1,2
1Institute of Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
Abstract:
Five base-stabilized beryllium Grignards of the type LBeBrY (L = IDipp (1,3-bis(diisopropylphenyl)imidazol-2-ylidene), IiPrMe (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), CDPPh (hexaphenylcarbodiphosphorane), Y = Dur (2,3,5,6-tetramethylphenyl = duryl); L = IiPrMe, Y = Tchp (2,4,6,-tricyclohexylphenyl); L = CAACMe (1-(2,6-diisopropylphenyl)-2,2,4,4-tetramethylpyrrolydin-5-ylidene, Y = Tmp (2,6-tetramethylpyrrolidine)) were synthesized by salt metathesis from LBeBr2 or ligand exchange at (Et2O)BeBrY. Single-crystal X-ray diffraction analyses show that the angle between the beryllium and carbon ligand planes depends mainly on L, varying from coplanar (L = CDPPh) to orthogonal (L = IDipp), via 50-70° for L = IiPrMe. In contrast, (CAACMe)BeBrDur and (CAACMe)BeBrTmp display coplanar and near-orthogonal arrangements, respectively. Energy decomposition analysis in combination with natural orbitals for chemical valence (EDA-NOCV) calculations rationalize these trends as arising from a balance of steric repulsion, stabilizing London dispersion interactions between L and Y, and small but non-negligible BeBrY→L (L = carbene) or L→BeBrY (L = CDPPh) π-donation components. Reduction of LBeBrAr led to complex product mixtures, presumably owing to Schlenk-type equilibria as well as the formation of highly reactive [LBeY]· and LBeHY intermediates involved in ligand decomposition reactions. Only the one-electron reduction of (CAACMe)BeBrTmp afforded a stable linear [(CAACMe)BeTmp]· radical, which EPR spectroscopy and DFT calculations indicate is a CAAC- rather than a Be-centered radical.
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