Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido ‐C 2 B 9 H 11 2− Ligand

• Published in: European journal of inorganic chemistry 2021-12, Vol.2021 (46), p.4868-4874
• Main Authors: Kaltenberg, Alexander A., Somov, Nikolay V., Malysheva, Yulia B., Vorozhtsov, Dmitry L., Grishin, Ivan D.
• Format: Article
• Language: English
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202100765

The reaction of the known closo ‐ruthenacarborane 3‐H‐3‐Cl‐3,3‐(PPh 3 ) 2 ‐ closo ‐3,1,2‐RuC 2 B 9 H 11 with tridentade nitrogen‐based ligands of the general formula (C 5 NH 4 CH 2 ) 2 NR (R=H, Me, Et, iPr, Bu t ) in benzene solution at 60 °C allowed us to isolate novel ruthenacarborane clusters 3,3,3‐(2’‐NC 5 H 4 CH 2 ) 2 NR‐ pseudocloso ‐3,1,2‐RuC 2 B 9 H 11 . According to the performed X‐ray study, the obtained compounds are the first examples of pseudocloso ‐metallacarboranes bearing unsubstituted C 2 B 9 2− nido ‐carborane ligand. In spite of the determined pseudocloso structure of the complexes in the solid state, the recorded 11 B{ 1 H} NMR spectra indicate that some of them are converted into the closo isomers in solution. The conducted quantum‐chemical calculations have confirmed the subtle difference between two configurations and possible rearrangement in solution. The performed electrochemical investigations show the ability of the formed ruthenacarboranes to undergo reversible oxidation to Ru(III) species.