441012-29-9Relevant academic research and scientific papers
RuII and RuIII Chloronitrile Complexes: Synthesis, Reaction Chemistry, Solid State Structure, and (Spectro)Electrochemical Behavior
Hildebrandt, Alexander,Kovalski, Eduard,Lang, Heinrich,Rüffer, Tobias,Scharf, Sebastian
, p. 1820 - 1833 (2020)
The synthesis of [Ti6O4(OiPr)8(O2CPh)8] (3) and [RuCl(N≡CR)5][RuCl4(N≡CR)2] (4a, R = Me; 4b, R = Ph), [Ru(N≡CPh)6][RuCl4(N≡CPh)2] (5) and [H3O][RuCl4(N≡CMe)2] (7a) is discussed. Crystallization of 5 from CH2Cl2 gave trans-[RuCl2(N≡CPh)4] (6). The solid-state structures of 3, 4a,b, 5, 6 and 7a are reported. Complex 4b forms a 3D network, while 6 displays a 2D structure, due to π-interactions between the benzonitrile ligands. The (spectro)electrochemical behavior of 4a,b and 6 was studied at 25 and –72 °C and the results thereof are compared with [NEt4][RuCl4(N≡CMe)2] (7b) and [RuCl(N≡CPh)5][PF6] (8). The electrochemical response of the cation and the anion in 4a,b are independent from each other. [RuCl(N≡CR)5]+ possesses one reversible RuII/RuIII process. However, [RuCl4(N≡CMe)2]– was shown to be prone to ligand exchange and disproportionation upon formation of either a RuIV and RuII species at 25 °C, while at –72 °C the rapid conversion of the electrochemically formed species is hindered. In situ IR and UV/Vis/NIR studies confirmed the respective disproportionation reaction products of the aforementioned oxidation and reduction, respectively.
