Synthesis and characterization of stable thiazolylazo anion radical complexes of ruthenium(II)

Abstract

Two stable thiazolylazo anion radical complexes of ruthenium(II), [Ru(L1 •-)(Cl)(CO)(PPh 3 ) 2 ] (1) and [Ru(L2 •-)(Cl)(CO)(PPh 3 ) 2 ](2) (where L1 = 2 0 -Thiazolylazo-2-imidazole and L2 = 4-(2 0 -Thiazolylazo)-1-n-hexadecyloxy-naphthalene), have been synthesized and characterized by spectroscopic and electrochemical techniques. The radical nature of the complexes has been confirmed from their room temperature magnetic moments and X-band ESR spectra. The radical complexes display a moderately intense (e * 10 4 M -1 cm -1 ) and relatively broad band in 430-460 nm region. In the microcrystalline state, complexes (1) and (2) display strong ESR signals at g = 1.951 and g = 1.988, respectively. In CH 2 Cl 2 solution, complexes (1) and (2) show a quasireversible one-electron response near -0.64 and -0.59 V, respectively, versus Ag/AgCl

Ruthenium-Catalyzed β-Alkylation of Secondary Alcohols and α-Alkylation of Ketones via Borrowing Hydrogen: Dramatic Influence of the Pendant N-Heterocycle

“…Liquid compounds were degassed by standard freeze−pump−thaw procedures prior to use. RuHCl(PPh 3 ) 3 (CO), 25 ethyl 6′-methoxy-[2,2′-bipyridine]-6-carboxylate, 23c 6-bromo-6′-methoxy-2,2′-bipyridine, 26 and benzylzinc bromide 27 were prepared as previously described, respectively. The 1 H and 31 P NMR spectra were recorded on a Bruker Avance 400 spectrometer.…”

Synthesis and Reactivity of Metal–Ligand Cooperative Bifunctional Ruthenium Hydride Complexes: Active Catalysts for β-Alkylation of Secondary Alcohols with Primary Alcohols

“…Liquid compounds were degassed by standard freeze−pump−thaw procedures prior to use. RuHCl(PPh 3 ) 3 (CO) 25 and L 1 −L 3 22a were prepared as previously described, respectively. The 1 H and 31 P NMR spectra were recorded on a Bruker Avance 400 spectrometer.…”

On the Electrochemical Reduction of 4‐(Thiazol‐2‐ylazo)‐Substituted 1‐Chloronaphthalenes: Formation and Characterization of Stable Radical Anions

“…The 1-halogen-substituted 4-(thiazol-2-ylazo) naphthalenes 4 a and 4 b used for this study were prepared by reaction of the known 4-thiazolylazo-substituted 1-naphthols [7] with POCl 3 in presence of DMF according to a published procedure. [6,8]…”