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Synthesis and characterization of new Pd(ii) and Pt(ii) complexes with 3-substituted 1-(2-pyridyl)imidazo[1,5-a]pyridine ligands

journal contribution
posted on 24.05.2021, 10:50 by Sara Pischedda, Sergio Stoccoro, Antonio Zucca, Giuseppe Sciortino, Fabrizio Ortu, Guy J Clarkson

Several palladium(II) and platinum(II) complexes (1–20) of general formula [M(Ln)(X)(Y)] [M = Pd, X = Y = Cl (1-Cl–4-Cl), X = Y = OAc (1-OAc–4-OAc); M = Pt: X = Y = Cl (5–8); M = Pd, X = Cl, Y = CH3 (9–12); M = Pt, X = Cl, Y = CH3 (13–16) or X = Y = CH3 (17–20); n = 1–4] have been synthesized by reaction of different Pd(II) and Pt(II) derivatives with various 3-substituted 1-(2-pyridyl)-imidazo[1,5-a]pyridines; i.e.Ln = 1-(2-pyridyl)-3-arylimidazo[1,5-a]pyridine (aryl = Phenyl, L1; 2-o-Tolyl, L2; Mesityl, L3) and 1-(2-pyridyl)-3-benzylimidazo[1,5-a]pyridine (L4). Detailed spectroscopic investigation (including IR, mono- and bi-dimensional 1H NMR) and elemental analysis has been performed for all these species, allowing their complete characterization. Ln act as N,N-bidentate ligands and coordinate the metal centers in a chelate fashion through the pyridyl (Npy) and the pyridine-like nitrogen atom of the imidazo[1,5-a]pyridine group (Nim). The X-ray structural analysis performed on two of Pd(II) and three Pt(II) complexes, namely [Pd(L2)(CH3)Cl] (10), [Pd(L3)(CH3)Cl] (11) and [Pt(L1)Cl2] (5), [Pt(L4)Cl2] (8), [Pt(L2)(CH3)Cl] (14) confirmed the spectroscopic and analytical data. Finally DFT studies unveiled the structural reasons behind the inertia of the synthesised compounds toward metalation, identified as the higher angle steric strain in comparison with the analogous bipyridine complexes.

History

Citation

Dalton Trans., 2021,50, 4859-4873

Author affiliation

Department of Chemistry

Version

AM (Accepted Manuscript)

Published in

Dalton Transactions: an international journal of inorganic chemistry

Volume

50

Issue

14

Pagination

4859 - 4873

Publisher

Royal Society of Chemistry

issn

1477-9226

eissn

1477-9234

Acceptance date

16/03/2021

Copyright date

2021

Available date

17/03/2022

Language

English