Intramolecular Oxidation of the Alcohol Functionalities in Hydroxyalkyl‐N‐Heterocyclic Carbene Complexes of Iridium and Rhodium

Benítez, Miriam; Mas‐Marzá, Elena; Mata, José A.; Peris, Eduardo

doi:10.1002/chem.201101187

Cited by 35 publications

(15 citation statements)

References 52 publications

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“…The M-C* (Table 2) are within the range reported in the literature for analogous Rh(III) and Ir(III) complexes with Cp* co-ligands. 12,32,[35][36][37][38][39] The M-C2 bond in complexes 4b, 4d and 5b with the small methyl substituent on the imidazolyl ring is significantly shorter than the equivalent bond in the analogous complexes with the mesityl substituent 4a, 4c and 5a ( Table 2). The longer M-C2 bond in complexes with a mesityl substituent is likely to be due to steric repulsion between the Cp* and the bulky mesityl group.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Cationic Rh and Ir complexes containing bidentate imidazolylidene–1,2,3-triazole donor ligands: synthesis and preliminary catalytic studies

et al. 2013

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A series of new cationic Rh(I), Rh(III) and Ir(III) complexes containing hybrid bidentate N-heterocyclic carbene–1,2,3-triazolyl donor of general formulae [Rh(CaT)(COD)]BPh4 (2a–d), [Rh(CaT)(CO)2]BPh4 (3a–d) and [M(CaT)(Cp*)Cl]BPh4 (M = Rh, 4a–d; M = Ir, 5a–c), where CaT = bidentate N-heterocyclic carbene–triazolyl ligands, COD = 1,5-cyclooctadiene and Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl, were synthesised. The imidazolium–1,2,3-triazolyl pre-ligands (1a–c and 1e–i) were readily prepared using the Cu(I) catalysed ‘click reaction’ between phenyl azide or benzyl azides with propargyl functionalised imidazolium salts. The single crystal solid state structures of complexes 2a–d; 3a–b; 4a–d and 5a–b confirm the bidentate coordination of the NHC–1,2,3-triazolyl ligand with the NHC coordinating via the ‘normal’ C2-carbon and the 1,2,3-triazolyl donor coordinating via the N3′ atom to form six membered metallocycles. These complexes are the first examples of Rh and Ir complexes containing the hybrid NHC–1,2,3-triazolyl ligands which exhibit a bidentate coordination mode. A number of these complexes showed limited efficiency as catalysts for the intramolecular hydroamination of 4-pentyn-1-amine to 2-methylpyrroline.

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Section: Dalton Transactions Papermentioning

confidence: 99%

Cationic Rh and Ir complexes containing bidentate imidazolylidene–1,2,3-triazole donor ligands: synthesis and preliminary catalytic studies

et al. 2013

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“…The high tendency of the N-hydroxyethyl group to undergo oxidation and cyclometalation with [Cp*IrCl 2 ] 2 in the presence of a weak base was also reported by Peris and co-workers. 78 Complexes 105a-c were obtained by the direct reaction of the corresponding hydroxyethyl-substituted azolium salts with [Cp*IrCl 2 ] 2 in refluxing methanol in the presence of Cs 2 CO 3 . Even when the less electrondonating triazolylidene ligand was used, the similar cyclometalated species 105d could be formed (Scheme 41).…”

Section: Cyclometalated [Cp*m(c^c)] Complexesmentioning

confidence: 99%

Cyclometalated [Cp*M(C^X)] (M = Ir, Rh; X = N, C, O, P) complexes

2014

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Half-sandwich Cp*Ir and Cp*Rh metalacycles have been successfully applied in traditional domains encompassing organic transformations and catalysis in recent years, especially the catalytic activation of C-H bonds. Cyclometalation has proven to be a highly attractive and versatile synthetic method for the formation of organometallic metalacycles. This review intends to describe isolated and well-defined cyclometalated iridium/rhodium complexes that contain a Cp*M-C (M = Ir, Rh) bond stabilised by the intramolecular coordination of neutral donor atoms (N, C, O or P). The formation of metalamacrocycles and cages employing cyclometalated approaches is discussed. In focusing on selected mechanistic insights garnered from iridium/rhodium-catalysed functionalisation of C-H bonds involving cyclometalated complexes, a limited number of substrates will be discussed, but a broad range of mechanistic features is highlighted.

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“…Examples of ruthenium complexes (numbered 1-5 as seen in Figure 1), produced by chelating NHCs bearing oxygen [9,10], phosphorous [11,12], allyl [13], sulphur [14] and nitrogen [15][16][17][18][19][20][21][22][23][24][25][26] moieties, have been used successfully as catalysts for the transfer hydrogenation reaction. Peris and coworkers reported on rhodium and ruthenium complexes derived from an NHC ligand functionalised with a pendant alcohol [27]. In our case, a bidentate NHC-Ru(II) complex with a tethered carboxylate group was obtained by transmetallation of silver(I)-NHC to ruthenium(II) in dry dichloromethane (DCM).…”

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confidence: 90%

Investigation of potential hybrid capacitor property of chelated N-Heterocyclic carbene Ruthenium(II) complex

Akkoç

Öz

Demirel

et al. 2018

Journal of Organometallic Chemistry

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The synthesis of chelated ruthenium(II) complex type Ru(η 6-HMB)(NHC)Cl (NHC=Nheterocyclic carbene, HMB=hexamethylbenzene) is presented. The ruthenium(II)-NHC complex 6 was obtained in good yield and was fully characterised by NMR spectroscopy, Xray diffraction and HRMS analysis. Electrochemical analysis by cyclic voltammetry (CV) revealed reversible redox behaviour at the ruthenium centre in 6. DFT studies and the catalytic activity of complex 6 on transfer hydrogenation reaction of aryl ketones are also presented. The potential hybrid capacitor applications of Ru-NHC complex is discussed and reported firstly in the literature. It was found that the highest performance was found at 20.1 F/g, which is a promising result for energy storage applications.

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Intramolecular Oxidation of the Alcohol Functionalities in Hydroxyalkyl‐N‐Heterocyclic Carbene Complexes of Iridium and Rhodium

Cited by 35 publications

References 52 publications

Cationic Rh and Ir complexes containing bidentate imidazolylidene–1,2,3-triazole donor ligands: synthesis and preliminary catalytic studies

Cationic Rh and Ir complexes containing bidentate imidazolylidene–1,2,3-triazole donor ligands: synthesis and preliminary catalytic studies

Cyclometalated [Cp*M(C^X)] (M = Ir, Rh; X = N, C, O, P) complexes

Investigation of potential hybrid capacitor property of chelated N-Heterocyclic carbene Ruthenium(II) complex

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