Synthesis and Electronic Structure of Ru2(Xap)4(Y-gem-DEE) Type Compounds: Effect of Cross-Conjugation

• Published in: Inorganic chemistry Vol. 54; no. 15; pp. 7645 - 7652
• Main Authors: Forrest, William P, Choudhuri, Mohommad M. R, Kilyanek, Stefan M, Natoli, Sean N, Prentice, Boone M, Fanwick, Phillip E, Crutchley, Robert J, Ren, Tong
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.08.2015
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.5b01315

Reported in this Article are the preparation and characterization of a series of new Ru2(II,III) compounds bearing one cross-conjugated σ-geminal-diethynylethene ligand (gem-DEE), namely, Ru2(Xap)4(Y-gem-DEE) (Xap = N,N′-anilinopyridinate (ap) or 2-(3,5-dimethoxy)­anilinopyridinate (DiMeOap), and Y = Si i Pr3 (1) or H (2)) and [Ru2(ap)4]2(μ-gem-DEE) (3). Compounds 1–3 were characterized by spectroscopic and voltammetric techniques as well as the single crystal X-ray diffraction study of 2a. The X-ray structural data of 2a and the spectroscopic/voltammetric data of compounds 1 and 2 indicate that the gem-DEE ligands are similar to simple alkynyls in their effects on the molecular and electronic structures of the Ru2(Xap)4 moiety. Similar to the previously studied [Ru2(ap)4]2(μ-C2n ) type compounds, dimer 3 exhibits pairwise 1e– oxidations and reductions, albeit the potential splits within the pair (ΔE 1/2) are significantly smaller than those of [Ru2(ap)4]2(μ-C4). The electronic absorption spectra of the reduced and oxidized derivatives of 1a and 3 were determined using spectroelectrochemistry methods. No discernible intervalence charge transfer transition (IVCT) was detected in the near-IR spectrum for either 3 – or 3 +, suggesting that the Ru2–Ru2 coupling in these mixed-valence states is weak. DFT calculations on a model compound of 3 yielded six singly occupied molecular orbitals (SOMOs), which have Ru2 contributions similar to those previously calculated for the [Ru2(ap)4]2(μ-C2n ) type compounds. Among six SOMOs, SOMO-2 is the only one containing substantial dπ–π­(gem-DEE) character across the entire Ru2-μ-gem-DEE-Ru2 linkage, which explains the weakened Ru2–Ru2 coupling.