title: Synthesis and Electronic Structure of Ru2(Xap)4(Y-gem-DEE) Type Compounds: Effect of Cross-Conjugation.
abstract: 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 (ΔE1/2) 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.
authors.affiliation: †Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
authors.forename: William P
authors.initials: WP
authors.lastname: Forrest
authors.affiliation: ‡Department of Chemistry, Carleton University, Ottawa, Ontario K1S 5B6, Canada.
authors.forename: Mohommad M R
authors.initials: MM
authors.lastname: Choudhuri
authors.affiliation: §Department of Chemistry and Biochemistry, University of Arkansas, Fayettesville, Arkansas 72701, United States.
authors.forename: Stefan M
authors.initials: SM
authors.lastname: Kilyanek
authors.affiliation: †Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
authors.forename: Sean N
authors.initials: SN
authors.lastname: Natoli
authors.affiliation: †Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
authors.forename: Boone M
authors.initials: BM
authors.lastname: Prentice
authors.affiliation: †Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
authors.forename: Phillip E
authors.initials: PE
authors.lastname: Fanwick
authors.affiliation: ‡Department of Chemistry, Carleton University, Ottawa, Ontario K1S 5B6, Canada.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Crutchley
authors.affiliation: †Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
authors.forename: Tong
authors.initials: T
authors.lastname: Ren