Study of complexes of platinum group metals containing nitrogen bases derived from pyridine aldehydes: Interesting molecular structures with unpredicted bonding modes of the ligands

A series of mono-cationic dinuclear half sandwich ruthenium, rhodium and iridium metal complexes have been synthesized using ((pyridin-2-yl)methylimino)nicotinamide (<b>L1</b>) and ((picolinamido)phenyl)picolinamide (<b>L2</b>) ligands: [(η⁶-arene)₂Ru₂ (μ-<b>L1</b>)Cl₃]⁺ (arene = C₆H₆, <b>1</b>; <i>p</i>-ⁱPrC₆H₄Me, <b>2</b>; C₆Me₆, <b>3</b>), [(η⁵-C₅Me₅)₂M₂(μ-<b>L1</b>)Cl₃] ⁺ (M = Rh, <b>4</b>; Ir, <b>5</b>), and [(η⁶-arene)₂Ru₂(μ-<b>L2</b>)(μ-Cl)]⁺ (arene = C₆H₆, <b>6</b>; <i>p</i>-ⁱPrC₆H₄Me, <b>7</b>; C₆Me₆, <b>8</b>), [(η⁵-C₅Me₅)₂M₂(μ-<b>L2</b>)Cl₂]⁺ (M = Rh, <b>9</b>; Ir, <b>10</b>). All the complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR and IR spectroscopy. The solid state structure of three representatives <b>4</b>, <b>6</b> and <b>9</b> has been determined by X-ray crystallographic studies. Interestingly, in the molecular structure of 4, the first metal is bonded to two nitrogen atoms whereas the second metal center is coordinated to only one nitrogen atom with two terminal chloride ligands. Fascinatingly in the case of the complexes with the symmetrical ligand <b>L2</b>, both ruthenium centers having η⁶-arene groups are bonded to nitrogen atoms with a bridging chloride atom between the two metal centers, whereas the metals with η⁵-Cp∗ groups are bonded to the ligand <i>N</i>,<i>O</i> and <i>N</i>,<i>N</i> fashion.