Synthesis, Characterization, and Surface Deposition of a Ruthenium(II) Complex with a Triphyrin(2.1.1) Ligand

The ruthenium(II) complex [RuCl(TriP)(CO)₂] (2) supported by a triphyrin(2.1.1) ligand (1) is synthesized and thoroughly characterized both in solution and deposited on a surface. Single crystal X‐ray diffraction indicated a slightly distorted octahedral geometry of 2 with a dome‐shaped structure of the Ru(II)‐TriP unit. Self‐assembled monolayers of 2 on Au(111) surfaces are prepared and investigated by infrared reflection absorption spectroscopy (IRRAS). A 15 cm⁻¹ shift of the carbonyl stretching modes to higher wavenumbers reflects electron withdrawal by the gold substrate and therefore static (de)activation of the complex 2. Moreover, the IRRAS data indicate a tilted adsorption geometry. X‐ray photoelectron spectroscopy confirms the formation of a chemically intact monolayer, and near‐edge X‐ray absorption fine structure spectroscopy further supports the hypothesis of a tilted adsorption geometry through the angular dependance of π* resonances at the carbon and nitrogen K‐edges. Mass spectrometry reveals chloride ligand exchange by dinitrogen following the ionization process. Attempts to replicate this reaction in condensed phase are unsuccessful.