Facile method for the synthesis of ruthenacarboranes, diamagnetic 3,3-[Ph2P(CH2)nPPh2]-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (n = 3 or 4) and paramagnetic 3,3-[Ph2P(CH2)nPPh2]-3-Cl-closo-3,1,2-RuC2B9H11 (n = 2 or 3), as efficient initiators of controlled radical polymerization of vinyl monomers

Cheredilin, D. N.; Dolgushin, Fedor M.; Гришин, И. Д.; Kolyakina, E. V.; Nikiforov, A. S.; Солодовников, С. П.; Il’in, M. M.; Даванков, В. А.; Chizhevsky, I. T.; Гришин, Д. Ф.

doi:10.1007/s11172-006-0394-9

Cited by 23 publications

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References 15 publications

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“…The starting complex 1 was obtained as described previously. [39] Isolation of products by column chromatography and their purification by recrystallization were carried out in air. Macherey-Nagel silica gel (230-400 mesh) was used for chromatography.…”

Section: Methodsmentioning

confidence: 99%

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: Methodsmentioning

confidence: 99%

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

et al. 2021

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Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

et al. 2017

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Analysis of the literature structures [(CO)(PPh3)2MC2B9H11] and [(CO)2(PPh3)MC2B9H11] suggests that in [L3MC2B9H11] metallacarboranes the trans influence of CO is greater than that of PPh3. Extending this study to the [L4MC2B9H11] system the new molybdacarboranes [3,3,3‐(CO)3‐3‐PPh3‐3,1,2‐closo‐MoC2B9H11] (2), [1,2‐Me2‐3,3,3‐(CO)3‐3‐PPh3‐3,1,2‐closo‐MoC2B9H9] (3) and trans‐[3,3‐(CO)2‐3,3‐(PPh3)2‐3,1,2‐closo‐MoC2B9H11] (4) were prepared and fully characterised. Consideration of the exopolyhedral ligand orientations (ELO) in 2 confirms that, in terms of trans influence, CO > PPh3 in [L4MC2B9H11] also. The ELO is effectively reversed in 3 through intramolecular steric crowding between the cage CH3 groups and the PPh3 ligand. The dicarbonylbis(triphenylphosphine) compound 4 has effective Cs symmetry with one CO ligand trans and the other CO ligand cis to the cage C–C connectivity. Unexpectedly the Mo–CO bond lengths are equal. DFT calculations on 4 reproduce this unusual result, but suggest that in the less‐crowded PH3 analogue, the Mo–CO bond length trans to cage C would be about 0.2 Å shorter than that trans to cage B. To test this prediction, the analogous PEt3 complex was prepared as cis and trans structural isomers 5 and 6. The cis isomer 5 is quantitatively converted into the trans isomer 6 when heated to reflux in THF. In 6 the Mo–CO bond more trans to cage C is about 0.2 Å shorter than that which is more trans to cage B, in line with the DFT prediction.

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

et al. 2019

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Facile method for the synthesis of ruthenacarboranes, diamagnetic 3,3-[Ph2P(CH2)nPPh2]-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (n = 3 or 4) and paramagnetic 3,3-[Ph2P(CH2)nPPh2]-3-Cl-closo-3,1,2-RuC2B9H11 (n = 2 or 3), as efficient initiators of controlled radical polymerization of vinyl monomers

Cited by 23 publications

References 15 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

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

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

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Facile method for the synthesis of ruthenacarboranes, diamagnetic 3,3-[Ph2P(CH2)nPPh2]-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (n = 3 or 4) and paramagnetic 3,3-[Ph2P(CH2)nPPh2]-3-Cl-closo-3,1,2-RuC2B9H11 (n = 2 or 3), as efficient initiators of controlled radical polymerization of vinyl monomers

Cited by 23 publications

References 15 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

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

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

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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