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• W4309844292 endingPage "20094" @default.
• W4309844292 startingPage "20087" @default.
• W4309844292 abstract "The synthesis of Pd complexes of the type [PdBr(iPr2-bimy)(NacAc)] (NacAc = β-ketiminate, iPr2-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene) was attempted, in a continuing effort to quantify donor abilities of chelating β-ketiminate ligands using the Huynh electronic parameter for bidentate donors (HEP2). Subtle variation of N-substituents on the NacAc backbone was discovered to induce a drastic change in the preferred chelating mode, in that the commonly encountered κ2-N,O-six-membered palladacycles were observed with R = Me and Et, while the unusual κ2-C,N-four-membered palladacycles were isolated with R = iPr, Cy, and tBu. Computational studies subsequently corroborated these findings, in the form of an overall exergonic six-to-four-membered ring contraction process and a lower associated activation energy for the three more electron-donating alkyl moieties. This trend in the established energy profiles can be attributed to a reduced HOMO–LUMO gap in the corresponding optimized structures of the six-membered ring complexes." @default.
• W4309844292 created "2022-11-29" @default.
• W4309844292 creator A5015288298 @default.
• W4309844292 creator A5025613672 @default.
• W4309844292 date "2022-11-24" @default.
• W4309844292 modified "2023-10-17" @default.
• W4309844292 title "Controlled Access to Four- and Six-Membered Palladacycles <i>via</i> Modifying Donor Abilities of β-Ketiminato Ligands (“NacAcs”)" @default.
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• W4309844292 doi "https://doi.org/10.1021/acs.inorgchem.2c03515" @default.
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