Catalytic C–C cross-coupling and hydrogen evolution by two Pd(II)-complexes of di-2-pyridyl ketone benzoyl hydrazones

Abstract

The reactions between [PdCl₂(CH₃CN)₂] and dpk-h [dpk-h = di-2-pyridyl ketone benzoyl hydrazone (dpkbh) or di-2-pyridyl ketone 4-aminobenzoyl hydrazone (dpk-4-abh)] at room temperature in air produced [PdCl₂(κ³-N_py,N_im,O-dpkbh)] (1) and PdCl₂(κ³-N_py,N_im,O-dpk-4-abh)] (2). X-ray structural analysis on a single crystal of PdCl(κ³-N,N,O-dpk-4-abh-H)]·H₂O·dmf (3) established its authenticity, points to keto-enol tautomerization due to solvent-compound interactions and revealed pseudo-coordination of the carbonyl group to the Pd ion. Solid-state infrared measurements confirmed the pseudo coordination of the carbonyl group of dpk-h as evident from the appearance of the ν(C=O) of coordinated dpk-h in close proximity to the ν(C=O) of uncoordinated dpk-h. ¹H NMR measurements on protophilic solutions of 1 and 2 disclosed solvent dependence and keto-enol tautomerization while variable temperature studies established the predominance of the keto form. The electronic absorption spectra of 1 and 2 measured in protophilic solvents confirmed the coordination of the Pd ion to dpk-h as evident from the appearance of d-d and ligand based electronic transitions. The catalytic C–C cross-coupling reactions and electro-catalytic behavior of 1 and 2 toward a proton reduction were investigated and revealed good catalytic properties. Overall rate constants (k_app) for the electrocatalytic H₂ evolution of (3.39 ± 0.3) × 10³ and (4.04 ± 0.2) × 10³ M⁻¹ s⁻¹ were estimated and overpotentials of 157 and 67 mV, and turnover numbers (TON) of 2.0 and 3.2 for 1 and 2, respectively, were determined.

Graphical Abstract

Keywords:

• Palladium
• catalysis
• C-C cross-coupling
• di-2-pyridyl ketone benzoyl hydrazones
• spectroscopy
• electrochemistry

Acknowledgement

The authors acknowledge Ms. Toni Johnson for NMR measurements.

Disclosure statement

No potential conflict of interest was reported by the authors.

Notes

1 The reaction rate constant, k_app (M^–1 s^–1), can be estimated from

$i_c=\mathit{nFA}[\text{cat}]\sqrt{D{k}_{\text{app}}[{\mathrm{H}}^{+}]}$ (1)

where n is the number of electrons, i_c is the plateau current (mA) at very fast scan rates, F is the Faraday’s constant (96,485 C mol^–1), A is the area of the electrode surface (cm²), [cat] is the bulk concentration of the catalyst (M), D is the diffusion coefficient (cm² s^–1) and [H⁺] is the bulk concentration of acid (M).

Additional information

Funding

This work was supported by the University of the West Indies for financial support.