Molecular Engineering of Redox Rich Diruthenium Compounds: Further Investigation of Ru2(Yap)4X Type Compounds

Further molecular engineering of diruthenium-(2-anilinopyridinate) alkynyl compounds through ligand design

“…1,3-Bis(trimethylsilyl)butadiyne was from GFS. Ru 2 (OAc) 4 Cl [19], Ru 2 (MeOap) 4 Cl [14], FcC"CH [20] and FcC"CC"CH [21] were prepared using the literature reported procedures. THF was distilled over Na/benzophenone under an N 2 atmosphere prior to use.…”

“…The solution color changed from green to brown immediately, and the reaction mixture was stirred for an hour. Removal of the solvents in vacuo yielded a brown residue, which was purified on a silica column deactivated by 10% Et 3 N in hexanes using a linear gradient of eluents (hexanes/ethyl acetate, 90/10-60/10, v/v) to afford analytically pure 2 (0.372 g, 65% based on Ru 14;H,4.92;N,8.92. Found: C,57.35;H,5.09;N,9.04%.…”

“…Table 2 Electrode potentials (V) of all observed redox couples in compounds 1-7 (1) 0.567 À0.750 1.317 Ru 2 (DiMeOap) 4 (C 4 TMS) (2) 0.491 À0.717 1.208 Ru 2 (DiMeOap) 4 (C 4 TMS) 2 (3) 0.915 À0.244 À1.348 Ru 2 (MeOap) 4 (C 4 TMS) (4) 0.500 À0.716 1.216 Ru 2 (MeOap) 4 (C 4 TMS) 2 (5) 0.988 À0.254 À1.362 Ru 2 (MeOap) 4 (C 2 Fc) (6) 0.416 À0.886 0.654 1.302 Ru 2 (ap) 4 (C 4 Fc) (7) 0.479 À0.762 0.707 1.241 a From Ref. [14].…”

“…Improved solubility of Ru 2 -alkynyl building blocks may also enable their incorporation into rigid rod polymers with interesting optoelectronic properties [13]. Two ap-derivatives, 2-(3-methoxyanilino)pyridinate (MeOap, Chart 1) and 2-(3-propoxyanilino)pyridinate were prepared by us, but only a marginal improvement in solubility was achieved [14]. Described in this contribution are the synthesis and characterization of a new ap-derivative, namely 2- (3,5-dimethoxyanilino)pyridine (HDiMeOap, Chart 1) and its Ru 2 -compounds including Ru 2 (DiMeOap) 4 Cl (1), Ru 2 (DiMeOap) 4 (C"CC"CSiMe 3 ) (2) and Ru 2 (DiMeOap) 4 (C"CC"CSiMe 3 ) 2 (3).…”

“…Ligand HDiMeOap was prepared from the reaction between 2-bromopyridine and 3,5-dimethoxyaniline using a procedure modified from that of HMeOap [14], and was characterized with 1 H NMR and mass spectroscopic techniques. Similar to the preparation of Ru 2 (ap) 4 Cl [4], Ru 2 (DiMeOap) 4 Cl (1) was obtained in satisfactory yield from the reaction of Ru 2 (OAc) 4 Cl with 7 equiv.…”