Syntheses, Crystal and Electronic Structures of Rhodium and Iridium Pyridine Di-Imine Complexes with O- and S-Donor Ligands: (Hydroxido, Methoxido and Thiolato)

Autor:	Michel Stephan, Max Völker, Matthias Schreyer, Peter Burger
Jazyk:	angličtina
Rok vydání:	2023
Předmět:	metal–ligand dπ-pπ-interaction Ir-O S bond dissociation enthalpies DFT P/LNO-CCSD(T) calculations oxidation state analysis metal–ligand charge transfer Chemistry QD1-999
Zdroj:	Chemistry, Vol 5, Iss 3, Pp 1961-1989 (2023)
Druh dokumentu:	article
ISSN:	2624-8549
DOI:	10.3390/chemistry5030133
Popis:	The syntheses of new neutral square-planar pyridine di-imine rhodium and iridium complexes with O- and S-donor (OH, OR, SH, SMe and SPh) ligands along with analogous cationic compounds are reported. Their crystal and electronic structures are investigated in detail with a focus on the non-innocence/innocence of the PDI ligand. The oxidation states of the metal centers were analyzed by a variety of experimental (XPS and XAS) and theoretical (LOBA, EOS and OSLO) methods. The dπ-pπ interaction between the metal centers and the π-donor ligands was investigated by theoretical methods and revealed the partial multiple-bond character of the M-O,S bonds. Experimental support is provided by a sizable barrier for the rotation about the Ir-S bond in the methyl thiolato complex and confirmed by DFT and LNO-CCSD(T) calculations. This was corroborated by the high Ir-O and Ir-S bond dissociation enthalpies calculated at the PNO-CCSD(T) level.
Databáze:	Directory of Open Access Journals
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