Revising the chemistry of κ2-dppe-closo-RuC2B9H11 fragment: Synthesis of novel diamagnetic complexes and its transformations

Zimina, Anastasiya M.; Knyazeva, N. A.; Balagurova, E. V.; Dolgushin, Fedor M.; Сомов, Н. В.; Vorozhtsov, D. L.; Malysheva, Yulia B.; Гришин, И. Д.

doi:10.1016/j.jorganchem.2021.121908

Cited by 9 publications

(9 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The The performed X-ray analysis has confirmed the closo-structure of the complex and incorporation of acetonitrile molecule into its structure (Figure 2). The Ru-N distance (2.064(2)Å) is typical for 18-e closo-ruthenacarboranes with nitrile ligands [4][5][6]. The structure of complex 3 provided on Figure 2 clearly shows that Xantphos ligand is symmetrically coordinated to the ruthenium atom in a k 2 -fashion.…”

Section: Synthesis Of Novel Ruthenacarboranesmentioning

confidence: 94%

Section: Synthesis Of Novel Ruthenacarboranesmentioning

confidence: 99%

“…A common way to produce ruthenacarboranes bearing chelate diphosphine ligands with wide bite angles is the reaction of the corresponding RuCl 2 (PPh 3 )(diphosphine) with the salt of the nido-carborane [4]. The reaction of the known RuCl 2 (PPh 3 )(Xantphos) [8] with K + [nido-7,8-C 2 B 9 H 12 ] − in benzene did not give the desired product neither at room temperature no on heating.…”

Section: Synthesis Of Novel Ruthenacarboranesmentioning

confidence: 99%

“…Its anisotropic EPR spectrum (see Figure S1) is typical for closo-ruthenacarboranes with 17 electrons at metal center. The MALDI mass spectrum recorded in negative mode contains an envelope-type signal of molecular anion 2 − at m/z = 847.4 typical for such compounds [4,5]. The structure of 2 was finally determined by X-ray diffraction study and is represented at Figure 1 while the general structural parameters are provided in Table 1.…”

Section: Synthesis Of Novel Ruthenacarboranesmentioning

confidence: 99%

“…Inorganics 2022, 10, x FOR PEER REVIEW 2 of 19 considered as intermediates in ATRP catalyzed by ruthenacarboranes [2]. The reduction of the aforementioned 17-e Ru(III) closo-complexes by amines in acetonitrile media allows obtaining 18-e Ru(II) species of the general formula 3,3-(P-P)-3-NCCH3-closo-3,1,2-RuC2B9H11 [4,5]. The mechanism of its formation assumes the formation of 16-e intermediates further stabilized by acetonitrile molecule.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

12-Vertex closo-3,1,2-Ruthenadicarbadodecaboranes with Chelate POP-Ligands: Synthesis, X-ray Study and Electrochemical Properties

et al. 2022

View full text Add to dashboard Cite

A class of so-called POP ligands (Xanthos, NiXantphos, DPEphos) are of a great interest to the coordination chemistry due to their wide P-M-P bite angles and ability to show either κ2- or κ3-binding modes. Such κ2–κ3-rearrangement is valuable for catalytic application and internal stabilization of intermediates. To widen the scope of ruthenium-based catalysts for Atom Transfer Radical Polymerization (ATRP) two new approaches to the synthesis of closo-ruthenacarboranes with aforementioned POP ligands were developed and six new 17-e (3,3-(POP)-3-Cl-closo-3,1,2-RuC2B9H11; 2, 4, 7) and 18-e (3,3-(POP)-3-NCCH3-closo-3,1,2-RuC2B9H11; 3, 5, 8) clusters were synthesized and characterized by means of NMR or ESR spectroscopy, MALDI mass-spectrometry and single crystal X-ray diffraction studies. The unique 18-e complex of Ru(II) with dioxygen ligand 3,3-(DPEphos)-3-(η2-O2)-closo-3,1,2-RuC2B9H11 (9) was isolated and characterized by X-ray diffraction. It was shown that aforementioned POP ligands coordinate to ruthenium by two phosphorus atoms in a κ2-fashion. The performed electrochemical studies have shown reversible Ru(II)-Ru(III) transition making the complexes suitable for application in catalysis of polymerization. The test experiments on methyl methacrylate (MMA) polymerization indicate the proceeding of the process in according with an ATRP mechanism.

show abstract

Section: Synthesis Of Novel Ruthenacarboranesmentioning

confidence: 94%

Section: Synthesis Of Novel Ruthenacarboranesmentioning

confidence: 99%