Ruthenium Diphosphine Closo-C2B9-Carborane Clusters with Nitrile Ligands: Synthesis and Structure Determination

Penkal, A. M.; Сомов, Н. В.; Shchegravina, Ekaterina S.; Гришин, И. Д.

doi:10.1007/s10876-019-01605-9

Cited by 6 publications

(8 citation statements)

References 43 publications

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“…The typical values for C c H 1 H chemical shift for closo ruthenacarboranes lie in the range from 1.5 to 3.5 ppm depending on auxiliary ligands. [19][20][21][22][23][24][25][26][27][28] At the same time the signals of protons of complexes 2-4 and 6 lie in the lower field area. The data provided in the Table 2 shows that the increase of the donating ability of alkyl substituent in complexes 3, 4, 6 (methyl, ethyl, tert.-butyl) results in a shielding of the C c À H resonances.…”

Section: Resultsmentioning

confidence: 95%

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

et al. 2021

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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 pseudoclosometallacarboranes bearing unsubstituted C 2 B 9 2À 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.

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Section: Resultsmentioning

confidence: 95%

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

et al. 2021

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“…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%

“…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%

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

et al. 2022

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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.

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Novel ruthenium(ii) and (iii) carborane complexes with diphosphine ligands and their application in radical polymerization

2020

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Ruthenium Diphosphine Closo-C2B9-Carborane Clusters with Nitrile Ligands: Synthesis and Structure Determination

Cited by 6 publications

References 43 publications

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

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

Novel ruthenium(ii) and (iii) carborane complexes with diphosphine ligands and their application in radical polymerization

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Ruthenium Diphosphine Closo-C2B9-Carborane Clusters with Nitrile Ligands: Synthesis and Structure Determination

Cited by 6 publications

References 43 publications

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C2B9H112− Ligand

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C2B9H112− Ligand

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

Novel ruthenium(ii) and (iii) carborane complexes with diphosphine ligands and their application in radical polymerization

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Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand