Bis‐Anagostic Structures in N,N’‐Chelate Ligand Complexes of Palladium(II)

Reaction of N,N’‐dibenzylidene‐2,2‐dimethylpropylenediamine with Pd(OAc)2 produces essentially one product which NMR spectroscopy indicates has a bis‐anagostic structure. A density functional theory (DFT) calculation shows that in the square planar structure, both aromatic rings lie above the coordi...

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Bibliographic Details
Published inEuropean journal of inorganic chemistry Vol. 2022; no. 12
Main Authors Sajjad, M. Arif, Schwerdtfeger, Peter, Cai, Yichao, Waters, Joyce M., Harrison, John A., Nielson, Alastair J.
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 27.04.2022
Subjects
Aromatic compounds
bis-Anagostic interactions
Coordination compounds
Crystallography
Cyclometallation reactions
C−H bond activation
Density functional theory
Hydrogen bonds
Inorganic chemistry
Ligands
Mathematical analysis
NMR spectroscopy
Oxygen atoms
Palladium
Planar structures
Spectrum analysis
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Summary:Reaction of N,N’‐dibenzylidene‐2,2‐dimethylpropylenediamine with Pd(OAc)2 produces essentially one product which NMR spectroscopy indicates has a bis‐anagostic structure. A density functional theory (DFT) calculation shows that in the square planar structure, both aromatic rings lie above the coordination plane with close approaches of two ortho‐C−H bond hydrogens to both the Pd centre and the two acetato ligand coordinating oxygen atoms. N,N’‐dibenzylideneethylenediamine reacts with Pd(OAc)2 similarly where a bis‐anagostic structure is indicated by NMR spectroscopy and a DFT calculation shows an energy preference for an above plane positioning of the two aromatic rings. N,N,N’,N’‐tetrabenzylethylenediamine reacts with Pd(OAc)2 to give a structure which X‐ray crystallography shows two benzyl phenyl groups lie above and below the coordination plane respectively. Chelating dibenzaldimine ligands on coordination to Pd(OAc)2 give 1H NMR spectra which indicate bis‐anagostic interactions of the aromatic ring ortho‐hydrogens with the palladium centre. DFT calculations show that in the solid state, both interactions occur above the coordination plane with one ortho‐hydrogen of each aromatic ring making close approaches to Pd and the adjacent acetato ligand coordinating oxygens.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202200027