Reactions of 5,6,10-{Cl(Ph3P)2Ru}-[5,6,10-(μ-H)3-10-H-exo-nido-7,8-C2B9H8] with bis(diphenylphosphino)methane and 1,2-bis(diphenylphosphino)benzene: specific features

• Published in: Russian chemical bulletin Vol. 72; no. 4; pp. 912 - 924
• Main Authors: Kaltenberg, A. A., Zimina, A. M., Bashilova, A. D., Malysheva, Yu. B., Vorozhtsov, D. L., Piskunov, A. V., Somov, N. V., Grishin, I. D.
• Format: Journal Article
• Language: English
• Published: New York Springer US 01-04-2023; Springer Nature B.V
• Subjects: Acetonitrile; Amines; Benzene; Carbon tetrachloride; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Articles; Hydrogen chloride; Inorganic Chemistry; Methane; Organic Chemistry; Oxidation; Phosphines; Ruthenium; Valence; ruthenacarboranes; cyclic voltammetry; bis(diphenylphosphino)methane; carboranes; 1,2-bis(diphenylphosphino)benzene
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-023-3854-9

Specific features of reactions of complex 5,6,10-{Cl(Ph
3
P)
2
Ru}-[5,6,10-(μ-H)
3
-10-H-
exo
-
nido
-7,8-C
2
B
9
H
8
] (
1
) with 1,2-bis(diphenylphosphino)benzene (dppbz) and bis(diphenylphosphino)methane (dppm) in acetonitrile in the presence of amines were studied. Novel
closo
-ruthenacarborane complexes containing the metal in a formal oxidation state of +2 were isolated. It was established that the reaction of
1
with dppbz affords a complex containing a coordinated acetonitrile molecule, whereas the reaction with dppm results in a tris(phosphine) complex with strongly sterically shielded ruthenium center. Reactions of the newly obtained compounds with carbon tetrachloride or hydrogen chloride give corresponding 17-electron complexes containing the metal atom in a formal oxidation state of +3. The reversibility of the Ru
II
→ Ru
III
redox transition in the compounds synthesized was investigated by cyclic voltammetry and the influence of the ligand environment on the values of the corresponding redox potentials was assessed.