Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence

Vinogradov, Mikhail M.; Nelyubina, Yulia V.; Loginov, Dmitry A.; Kudinov, Alexander R.

doi:10.1016/j.jorganchem.2015.04.007

Cited by 17 publications

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“…Following these reflections, it would be logical to suggest that metallacarboranes with the metal atom in the high oxidation state will have reduced ability to undergo the cage rearrangements due to acceptor properties of the metal atom. In order to verify this hypothesis, we have studied the thermal stability of the previously synthesized Ir(III) complex [1,2-Me 2 -3-(Cp)-4-SMe 2 -3,1,2- closo -IrC 2 B 9 H 8 ]PF 6 . This compound was recovered unchanged after its reflux in tetrachloroethane (146 °C) for 2 h. Its derivative with more electron-donating and sterically crowded pentamethylcyclopentadienyl ligand iridacarborane [1,2-Me 2 -3-(Cp*)-4-SMe 2 -3,1,2 -closo -IrC 2 B 9 H 8 ]NO 3 ( 7 NO 3 ) was prepared by an interaction of the dimeric iridium chloride [Cp*IrCl 2 ] 2 with thallium salt Tl[7,8-Me 2 -9-SMe 2 -7,8- nido -C 2 B 9 H 8 ] in the presence of TlNO 3 (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 99%

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me₂-X-SMe₂-7,8-nido-C₂B₉H₈]⁻ (X = 9 and 10)

et al. 2017

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Polyhedral rearrangement of iridacarborane 1,2-Me2-3,3-(cod)-4-SMe2-3,1,2-closo-IrC2B9H8 (1) proceeds in a solution at RT and affords a product of 1,2 → 1,7 isomerization 1,8-Me2-2,2-(cod)-7-SMe2-2,1,8-closo-IrC2B9H8 (2). Rhodium derivative 1,2-Me2-3,3-(cod)-4-SMe2-3,1,2-closo-RhC2B9H8 (3) is significantly more stable toward heating than iridium complex 1 and isomerizes at 110 °C by 1,2 → 1,2 and 1,2 → 1,7 reaction schemes with 1,2 → 1,2 being the predominant route forming 1,2-Me2-4,4-(cod)-8-SMe2-4,1,2-closo-RhC2B9H8 (4) and 1,8-Me2-2,2-(cod)-7-SMe2-2,1,8-closo-RhC2B9H8 (5). Complexes 4 and 5 were characterized by 11B{1H}–11B{1H} COSY NMR spectrometry. A mechanism of 1,2 → 1,2 isomerization of 3 to 4 was proposed on the basis of DFT calculations. Reaction of the thallium salt Tl[7,8-Me2-9-SMe2-7,8-nido-C2B9H8] (CarbTl) with [Cp*RuCl]4 in THF furnishes new ruthenacarborane 1,2-Me2-3-(Cp*)-4-SMe2-3,1,2-closo-RuC2B9H8 (6). Heating of 6 at 80 and 144 °C leads to the partial and complete decomposition, respectively. Interaction of CarbTl with [Cp*IrCl2]2 in the presence of TlPF6 provides two new Ir(III) complexes [1,2-Me2-3-(Cp*)-4-SMe2-3,1,2-closo-IrC2B9H8]PF6 (7PF6) and 1,2-Me2-3-(Cp*)-4-SMe-3,1,2-closo-IrC2B9H8 (8) both stable upon heating in boiling tetrachloroethane (146 °C). A new 10-substituted charge-compensated carborane [7,8-Me2-10-SMe2-7,8-nido-C2B9H9] (9) was synthesized via an interaction of dicarbollide dianion [7,8-Me2-7,8-nido-C2B9H9]2– with dimethyl sulfide and acetaldehyde in acidic media. Thallium salt of 9 Tl[7,8-Me2-10-SMe2-7,8-nido-C2B9H8] (10) reacts with [(cod)IrCl]2 furnishing positional isomer of 1 with a symmetrical emplacement of SMe2 substituent complex 1,2-Me2-3,3-(cod)-8-SMe2-3,1,2-closo-IrC2B9H8 (11). Iridacarborane 11 requires elevated temperatures to undergo cage isomerization and converts upon heating at 110 °C to two new compounds 1,8-Me2-2,2-(cod)-11-SMe2-2,1,8-closo-IrC2B9H8 (12) and 1,2-Me2-4,4-(cod)-9-SMe2-4,1,2-closo-IrC2B9H8 (13) as a result of 1,2 → 1,7 and 1,2 → 1,2 rearrangements respectively with 13 being the minor product. The structures of 2, 6, 7PF6, 8, 10, 12, and 13 were determined by single-crystal X-ray diffraction.

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Section: Results and Discussionmentioning

confidence: 99%

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me₂-X-SMe₂-7,8-nido-C₂B₉H₈]⁻ (X = 9 and 10)

et al. 2017

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“…The cleavage of C c À C c bond results in the tetragonal open face C1À RuÀ C2À B6 and distortion of the carborane cage. In spite of the examples of such type of metallacarboranes are known for years, [8][9][10][11][12][13][14][15][16][17][18] the obtained complexes exhibit the first examples of pseudocloso metallacarboranes based on unsubstituted C 2 B 9 H 11 2À , thus its formation was much unexpected.…”

Section: Resultsmentioning

confidence: 96%

“…The SMe 2 substituted rhoda-and iridacarboanes obtained in Kudinov's group also confirm the discussing proposition. [8,9] The 16-valence-electron complexes [M(η-9-SMe 2 -7,8-Me 2 -7,8-C 2 B 9 H 8 )X 2 ] (M=Rh, Ir; X=Cl, Br, I) exist in pseudocloso state, while its cyclooctadienyl derivatives 16-e complexes [M(η-9-SMe 2 -7,8-Me 2 -7,8-C 2 B 9 H 8 )(cod)] or 18-electron complexes [M(η-9-SMe 2 -7,8-Me 2 -7,8-C 2 B 9 H 8 )X 2 (SMe 2 )] are closo-metallacarboranes.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3] Contrary to Cp dicarbollide dianion bears double negative charge which makes it possible to stabilize higher oxidation states of transition metals which may be useful in some cases. Another peculiarity of the dicarbollide ligand is the observed possibility of elongation of the bond between carbon atoms of carborane cage (C c À C c ) leading to the formation of hypercloso (or isocloso), [4][5][6] arachno [7] or pseudocloso [8][9][10][11][12][13][14] complexes. Hypercloso and arachno-metallacarboranes have respectively fewer or extra skeletal pairs while pseudocloso ones are isoelectronic to closo complexes.…”

Section: Introductionmentioning

confidence: 99%

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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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“…The replace-ment of the SMe 2 group with NMe 3 one in the carborane ligand of the catalyst led to a signifi cantly increased yield of 4a (up to 62% according to 1 H NMR data; see Table 1, entry 2). The observed eff ect may be explained by the affi nity of SMe 2 group to demethylation processes even in the presence of very weak nucleophiles (e.g., halide ions) to give sulfi de derivatives, 33 in which the SMe group can hinder the proceeding of catalytic processes. In particular, we have previously reported 34 that the iron methyl sulfi de complex (9-SMe-7,8-C 2 B 9 H 10 )Fe(C 6 H 6 ) does not undergo arene exchange reactions due to the presence of an intramolecular S−Fe interaction in the intermediate (9-SMe-7,8-C 2 B 9 H 10 )Fe.…”

Section: Resultsmentioning

confidence: 99%

Trimethylammonium-containing rhodacarborane [(9-NMe3-7,8-C2B9H10)RhCl2]2 as a catalyst for the annulation of arylcarboxylic acids with alkynes

2021

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Rhodacarborane [(9-NMe 3 -7,8-C 2 B 9 H 10 )RhCl 2 ] 2 exhibited moderate catalytic activity in the reaction of annulation of arylcarboxylic acids with alkynes, giving naphthalenes as the major products. Eff ects of the substituent at the carborane ligand, as well as the nature of organic substrates, on the catalytic activity and selectivity of the reaction were estimated. In particular, it was revealed that a replacement of the NMe 3 group at the carborane ligand with the SMe 2 one leads to a signifi cantly decreased activity of the catalyst.

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Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence

Cited by 17 publications

References 50 publications

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me₂-X-SMe₂-7,8-nido-C₂B₉H₈]⁻ (X = 9 and 10)

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me₂-X-SMe₂-7,8-nido-C₂B₉H₈]⁻ (X = 9 and 10)

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

Trimethylammonium-containing rhodacarborane [(9-NMe3-7,8-C2B9H10)RhCl2]2 as a catalyst for the annulation of arylcarboxylic acids with alkynes

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Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence

Cited by 17 publications

References 50 publications

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me2-X-SMe2-7,8-nido-C2B9H8]− (X = 9 and 10)

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me2-X-SMe2-7,8-nido-C2B9H8]− (X = 9 and 10)

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

Trimethylammonium-containing rhodacarborane [(9-NMe3-7,8-C2B9H10)RhCl2]2 as a catalyst for the annulation of arylcarboxylic acids with alkynes

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Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me₂-X-SMe₂-7,8-nido-C₂B₉H₈]⁻ (X = 9 and 10)

Polyhedral Rearrangements in the Complexes of Rhodium and Iridium with Isomeric Carborane Anions [7,8-Me₂-X-SMe₂-7,8-nido-C₂B₉H₈]⁻ (X = 9 and 10)

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