Multifunctional Behavior by a Bis-(phosphinimino)methanide Ligand: η2- vs η3-coordination vs Bronsted Basicity
- 10 February 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (8) , 2312-2313
- https://doi.org/10.1021/ja039711y
Abstract
The reaction of [(Cymene)RuCl2]2 with the chelate LiHC(PPh2NPh)2 occurs to remove both chloride ligands, to furnish a cationic Ru(II) complex with the monoanionic ligand bound η3, through two N and an sp3 carbon. This cation is also produced from the conjugate acid of the ligand H2C(PPh2NPh)2 because this molecule can serve as a Brønsted base, to deprotonate the acidic carbon of another molecule of H2C(PPh2NPh)2. DFT calculations show an energy surface where (Cymene)RuHC(PPh2NPh)2L is more stable with a Ru−CH(PPh2NPh)2 bond and with L = Cl- or MeCN not coordinated to Ru, than to an η2-HC(PPh2NPh)2 structure with coordinated L; this is tested experimentally. The greater tendency for this ligand to be coordinated η3 vs analogous diketiminates is discussed. The nucleophilicity of Cγ in structure 1, vs that of donors L = Cl- or MeCN, is evaluated to understand the preference of the bis(phosphinimino)methanide to be bidentate or tridentate.Keywords
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