Controlled Access to Four- and Six-Membered Palladacycles via Modifying Donor Abilities of ß-Ketiminato Ligands ("NacAcs").
Inorg Chem
; 61(49): 20087-20094, 2022 Dec 12.
Article
em En
| MEDLINE
| ID: mdl-36419368
ABSTRACT
The synthesis of Pd complexes of the type [PdBr(iPr2-bimy)(NacAc)] (NacAc = ß-ketiminate, iPr2-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene) was attempted, in a continuing effort to quantify donor abilities of chelating ß-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.
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Ano de publicação:
2022
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Article