Differentiating Two Nitrosylruthenium Isomeric Complexes by Steady-State and Ultrafast Infrared Spectroscopies.

Abstract

The [Ru(II)-NO+] group affects the structure and chemical reactivity of nitrosylruthenium(II) complexes. A characteristic infrared absorption band due to the nitrosyl (NO) stretching motion is shown in the frequency region 1800-1900 cm-1. In this work, linear infrared (IR) and nonlinear IR methods, including pump-probe and two-dimensional (2D) IR, were utilized to study the structures and dynamics of two isomeric nitrosylruthenium complexes [Ru(OAc)(2mqn)2NO] (H2mqn = 2-methyl-8-quinolinol) in cis and trans isomeric configurations in a weak polar solvent (CDCl3). Using the NO stretching mode as a vibrational probe, information about local structural dynamics of the Ru complex as well as solvent fluctuation dynamics was obtained. In particular, a "structured" solvent environment is believed to form in the vicinity of the NO group in the case of the cis isomer with the aid of a neighboring OAc ligand, which is the reason for more efficient vibrational relaxation but more inhomogeneously distributed solvent and thus associated slower spectral diffusion. Our results also suggest a more anharmonic potential surface for the NO stretching mode in the less stable trans isomer.