RuII and RuIII Chloronitrile Complexes: Synthesis,Reaction Chemistry,Solid State Structure,and (Spectro)Electrochemical Behavior |
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| Authors: | Sebastian Scharf Eduard Kovalski Tobias Rüffer Alexander Hildebrandt Heinrich Lang |
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| Institution: | Inorganic Chemistry, Faculty of Natural Sciences, Institute of Chemistry, Technische Universität Chemnitz, 09107 Chemnitz, Germany |
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| Abstract: | 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. |
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| Keywords: | Ruthenium(II)/(III) Titanium Nitrile Chloro Solid-state structures (Spectro)electrochemistry |
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