Coordination of Palladium with Polydentate Non‐planar Ligands with Competitive Donors (Oxygen and Double Bonds). Role of Stereochemistry

Palladium (II) complexes of three polydentate non‐planar bicyclo[4.4.0]decane ligands with at least one double bond and bridgehead cis‐substituents CH2OH or CH2OCH2 were prepared in order to investigate the role of stereochemistry and donor nucleophilicity in the Pd coordination. All ligands and the...

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Bibliographic Details
Published in:ChemistrySelect (Weinheim) 2024-01, Vol.9 (4), p.n/a
Main Authors: Hirtopeanu, Anca, Stanescu, Michaela Dina, Filip, Petru, Tintaru, Aura, Stavarache, Cristina, Maganu, Maria, Oprea, ▪ Ovidiu
Format: Article
Language:English
Subjects:
Computational chemistry
Coordination mode
Ligand effects
Palladium
Solid-state NMR spectroscopy
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Summary:Palladium (II) complexes of three polydentate non‐planar bicyclo[4.4.0]decane ligands with at least one double bond and bridgehead cis‐substituents CH2OH or CH2OCH2 were prepared in order to investigate the role of stereochemistry and donor nucleophilicity in the Pd coordination. All ligands and their corresponding complexes were characterized using NMR, solid‐state NMR (ssNMR), HR‐MS, ATR‐IR, DSC‐TGA. For ligand cis‐1,4,5,8‐tetrahydro‐naphthalene‐4a,8a‐diyl‐dimethanol (L2) the X‐ray structure corresponded to the DFT optimised structure. The HR‐MS and thermal analysis data confirmed a complexation ratio: ligand/PdCl2 of 1/1. The experimental data as well as the computations are consistent with the structures proposed based on 13C‐ssNMR, namely palladium coordinates with one double bond and an oxygen atom for ligands with CH2OH groups and with both double bonds for the ligand with an etheric bridge, showing the prevalence of stereochemistry over donor nucleophilicity for such non‐planar ligands. Non‐planar unsaturated cis‐decaline ligands with bridgehead CH2OH (L1, L2) or CH2OCH2 substituents (L3) have been synthesized and their Pd(II) complexes were prepared. The structures have been established using solid‐state NMR, NMR, ATR‐IR, HR‐MS and were confirmed by DFT calculations. The complexation occurs with stereochemical control which prevails over the nucleophilicity of the donor (oxygen and double bond).
ISSN:2365-6549
2365-6549
DOI:10.1002/slct.202301768