Portal de Periódicos da CAPES

Ru II and Ru III Chloronitrile Complexes: Synthesis, Reaction Chemistry, Solid State Structure, and (Spectro)Electrochemical Behavior

2020; Wiley; Volume: 646; Issue: 22 Linguagem: Inglês

10.1002/zaac.202000304

1521-3749

Sebastian Scharf, Eduard Kovalski, Tobias Rüffer, Alexander Hildebrandt, Heinrich Lang,

Metal-Catalyzed Oxygenation Mechanisms

The synthesis of [Ti 6 O 4 (O i Pr) 8 (O 2 CPh) 8 ] ( 3 ) and [RuCl(N≡CR) 5 ][RuCl 4 (N≡CR) 2 ] ( 4a , R = Me; 4b , R = Ph), [Ru(N≡CPh) 6 ][RuCl 4 (N≡CPh) 2 ] ( 5 ) and [H 3 O][RuCl 4 (N≡CMe) 2 ] ( 7a ) is discussed. Crystallization of 5 from CH 2 Cl 2 gave trans ‐[RuCl 2 (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 [NEt 4 ][RuCl 4 (N≡CMe) 2 ] ( 7b ) and [RuCl(N≡CPh) 5 ][PF 6 ] ( 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 Ru II /Ru III process. However, [RuCl 4 (N≡CMe) 2 ] – was shown to be prone to ligand exchange and disproportionation upon formation of either a Ru IV and Ru II 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.