Manganа- and rhena-copper carboranes based on the medium-size non-icosahedral 5,6-dicarba-nido-decaborane

Reaction of the deprotonated medium-size non-icosahedral carborane 5,6-nido-C2B8H12 (1) with Re(CO)5Cl affords tricarbonyl anionic complexes of Re [1,1,1-(CO)3-isonido-1,2,4-ReC2B8H10]- as PPh4- 3a and tmndH- 3b salts (tmnd — N,N,N′,N′-tetramethyl-1,8-diaminonaphtaline). Treatment of [tmndH][1,1,1-(CO)3-isonido-1,2,4-MC2B8H10]- (M = Mn 2b, Re 3b) with the equivalent amount of CuCl and PPh3 in CH2Cl2 leads to formation of two isomers of bimetallic complexes [1,3,7(6)-{Cu(PPh3)}-3,7(6)-μ-H2-1,1,1-(CO)3-isonido-1,2,4-MC2B8H8] (M = Mn 4, Re 5) with two B-H⋯Cu bonds. All newly obtained compounds were characterized by a combination of analytical and multinuclear NMR spectroscopic data and IR spectroscopy. The structures of complexes 3b and 4 were researched by X-ray diffraction studies. The nature of interaction between {Cu(PPh3)} and mangana-carborane fragments was clarified based on the computed electron density critical points (within QTAIM framework) and Density Overlap Regions Indicator (DORI) distributions. Transition state between the two diastereomers of 4 was located, the isomerization rate was found to be of order of 1 s−1. © 2020 Elsevier B.V.

Balagurova E.V.1 , Dolgushin F.M.1 , Medvedev M.G.1, 2, 3, 4 , Kononova E.G.1 , Godovikov I.A.1 , Smol′yakov A.F. 1, 5 , Chizhevsky I.T.1
  • 1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Science, 28 Vavilov Str, Moscow, 119991, Russian Federation
  • 2 N. D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences, Leninsky Prospect 47, Moscow, 119991, Russian Federation
  • 3 National Research University Higher School of Economics (HSE), Myasnitskaya Str. 20, Moscow, 101000, Russian Federation
  • 4 Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow, 119991, Russian Federation
  • 5 Faculty of Science, RUDN University, 6 Miklukho-Maklaya Street, Moscow, 117198, Russian Federation
Ключевые слова
Binuclear mangana- and rhenacarborane clusters; Crystal structure; IR spectroscopy; NMR spectroscopy; Synthesis; Tricarbonyl carborane complexes
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