Binuclear rhodium(III) and iridium(III) monoselenocarboxylates: Synthesis, spectroscopy and structure of an ortho-metallated iridium complex featuring an IrCCC(μ-Se) chelate ring

Kumbhare, Liladhar B.; Wadawale, Amey; Jain, Vimal K.; Sieger, Monika; Kaim, Wolfgang

doi:10.1016/j.inoche.2010.01.012

Cited by 9 publications

(5 citation statements)

References 30 publications

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“…26 The Rh−C(Cp* centroid) distances of complexes 2 and 3 are in the normal range: 1.784(1)− 1.786(1) Å. 25 The Ir−Se bond distance (2.4822(15) Å) in 6 is longer than the values reported for the complex [η 5 -Cp*Ir-{Se 2 C 2 (CO 2 Me) 2 }] (2.3494(7) and 2.3520(7) Å) 27 and is consistent with the distances reported for [(η 5 -Cp*)Ir(2arylselenomethyl)pyridine)Cl][PF 6 ] (2.453(1) Å), 16 [η 5 -Cp* IrCl(μ -SeCOC 6 H 5 )(κ 2 -SeCOC 6 H 4 )Ir(η 5 -Cp* )] (2.445(2)−2.495(1) Å), 28 and [η 5 -Cp*Ir(μ 3 -Se) 2 {PtTol-(PPh 3 )} 2 ] (2.416(1)−2.422(1) Å). 29 The Ir−N bond length of 6 (2.094(10) Å) is similar to that of [(η 5 -Cp*)Ir(2arylthiopyridyl) pyridine)Cl][PF 6 ] (2.099(8) Å) 16 and shorter than the values reported for Ir(III) complexes of the pyridinetriazole ligand (2.137( 5) Å) 15a and 2-(1-benzyl-1H-1,2,3triazol-4-yl)pyridine (2.151(2)−2.159(7) Å).…”

Section: ■ Results and Discussionsupporting

confidence: 89%

Catalyst Activation with CpRh^III/Ir^III–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

et al. 2014

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The reactions of 1-benzyl-4-((phenylthio/phenylseleno)methyl)-1H-1,2,3-triazole (L1/L2) and 4-phenyl-1-((phenylthio/phenylseleno)methyl)-1H-1,2,3-triazole (L3/L4), synthesized using the click reaction, with [(η5-Cp*)RhCl(μ-Cl)]2 and [(η5-Cp*)IrCl(μ-Cl)]2 at room temperature followed by treatment with NH4PF6 result in complexes of the type [[(η5-Cp*)M(L)Cl] (1–8). Their HR-MS and 1H, 13C{1H}, and 77Se{1H} NMR spectra have been found characteristic. The single-crystal structures of 2, 3, and 6 have been established by X-ray crystallography. There is a pseudo-octahedral “piano-stool” disposition of donor atoms around Rh/Ir. In 1, 2, 5, and 6 N(3) of the triazole skeleton coordinates with Rh/Ir, whereas in the other four complexes the nitrogen involved is N(2). These complexes have been explored as catalysts for N-methylmorpholine N-oxide (NMO) based and Oppenauer-type oxidation of alcohols and transfer hydrogenation (TH) of carbonyl compounds with 2-propanol. Oppenauer type oxidation is somewhat slower than that based on NMO. The homogeneous nature of TH is supported by a poisoning test. The catalytic processes are more efficient with Rh complexes than the corresponding Ir complexes. The complexes having N(2) coordinated with the metal have shown better activity than those in which N(3) is involved in ligation. The reactivity with respect to ligands is in the order Se > S. In TH the species formed with loss of Cp* appears to be involved in catalysis with Rh as well as Ir complexes. Such a loss is noticed in the case of Rh for the first time. Generally results of DFT calculations are consistent with the experimental results.

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Section: ■ Results and Discussionsupporting

confidence: 89%

Catalyst Activation with CpRh^III/Ir^III–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

et al. 2014

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“…The Ir–S bond distances of 3 [2.3640(7) and 2.3694(8) Å] are within the range [2.318(1)–2.3872(10) Å] in which such bond lengths of [η 5 -Cp*Ir-(CO)(μ-STol)Pt(STol)(PPh 3 )], [η 5 -Cp*Ir(η 2 -ppy-S- p -tol)(H 2 O)][OTf] 2 , [η 5 -Cp*Ir(4,6-di- t -butyl-(2-methylthiophenylimino)- o -benzoquinone][PF 6 ].CH 2 Cl 2 , [η 5 -Cp*Ir( n BuPPh 2 )({7-(S)PPh 2 }-8-S-7,8-C 2 B 9 H 10 )], and [η 5 -Cp*IrCl{2-(phenylthiomethyl)pyridine}]PF 6 have been reported. The Ir–Se bond distances in 4 [2.4922(13) and 2.4547(12) Å] are consistent with the values reported for [η 5 -Cp*IrCl{2-(phenylselenomethyl)pyridine}]PF 6 [2.4531(10) Å], [η 5 -Cp*IrCl(μ-SeCOC 6 H 5 )(κ 2 -SeCOC 6 H 4 −)Ir(η 5 -Cp*)] [2.445(2)– 2.495(1) Å], and [η 5 -Cp*Ir(μ 3 -Se) 2 {PtTol(PPh 3 )} 2 ] [2.416(1)–2.422(1) Å] but longer than the values reported for [η 5 -Cp*Ir{Se 2 C 2 (CO 2 Me) 2 }] [2.3494(7) and 2.3520(7) Å] . The Ir−η 5 -Cp*(centroid) distances (Å) in 3 [1.814(1)] and 4 [1.812(8)] are normal and consistent with the values reported for complex [(η 5 -Cp*)Ir(phpy)Cl] [1.863 Å] .…”

Section: Resultssupporting

confidence: 81%

Half-Sandwich Rhodium/Iridium(III) Complexes Designed with Cp* and 1,2-Bis(phenylchalcogenomethyl)benzene as Catalysts for Transfer Hydrogenation in Glycerol

et al. 2014

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The reactions of 1,2-bis(phenylthiomethyl)benzene(L1) and 1,2-bis(phenylselenomethyl)benzene(L2) with [(η 5 -Cp*)MCl(μ-Cl)] 2 (M = Rh or Ir) at room temperature, followed by treatment with NH 4 PF 6 have resulted in air and moisture insensitive half-sandwich complexes of composition [(η 5 -Cp*)M(L)Cl]-[PF 6 ] (Rh, 1−2; Ir, 3−4; L = L1 or L2). Their HR-MS, 1 H, 13 C{ 1 H}, and 77 Se{ 1 H} NMR spectra were found to be characteristic. The single crystal structures of 1−4 have been established by X-ray crystallography. The complexes 1−4 have been found efficient for catalytic transfer hydrogenation (TH) of aldehydes and ketones in glycerol, which acts as a solvent and hydrogen source. Complexes 1−2 are the first examples of Rh species explored for TH in glycerol. The catalysis appears to be homogeneous. The complexes of the (Se, Se) ligand are marginally efficient than the corresponding complexes of the (S, S) ligand. The reactivity of Rh complexes in comparison to those of Ir also appears to be somewhat more. The results of DFT calculations appear to be generally consistent with experimental catalytic efficiencies and bond lengths/angles.

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“…In the case of complex 48, the Ir–Se bond distance value was 2.4822 Å, which was longer than the values obtained for the complex [η 5 -Cp*Ir-{Se 2 C 2 (CO 2 Me) 2 }] (2.3494 and 2.3520 Å) 203 and near to the distances reported for [(η 5 -Cp*)Ir((2-arylselenomethyl)pyridine)Cl][PF 6 ] at 2.453 Å, 197 [η 5 -Cp*IrCl(μ-SeCOC 6 H 5 )(κ 2 -SeCOC 6 H 4 )Ir(η 5 -Cp*)] at 2.445–2.495 Å, 204 and [η 5 -Cp*Ir(μ 3 -Se) 2 {PtTol-(PPh 3 )} 2 ] at 2.416–2.422 Å. 205 Moreover, the Ir–N bond distance was 2.094 Å, which was very close to the Ir–N bond length in [(η 5 -Cp*)Ir(2-arylthiopyridyl) pyridineCl][PF 6 ] at 2.099 Å ( ref.…”

Section: Structural Properties and Frontier Molecular Orbital Analysi...supporting

confidence: 62%

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

2018

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In recent years, metal complexes of organo 1,2,3-triazole click-derived ligands have attracted significant attention as catalysts in many chemical transformations and also as biological and pharmaceutical active agents. Regarding the important applications of these metal-organo 1,2,3-triazole-based complexes, in this review, we focused on the recently reported investigations of the structural, electronic, and spectroscopic aspects of the complexation process in transition metal complexes of 1,2,3-triazole-based click ligands. In line with this, the coordination properties of these triazole-based click ligands with transition metals were studied via several quantum chemistry calculations. Moreover, considering the complexation process, we have presented comparative discussions between the computational results and the available experimental data.

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Binuclear rhodium(III) and iridium(III) monoselenocarboxylates: Synthesis, spectroscopy and structure of an ortho-metallated iridium complex featuring an IrCCC(μ-Se) chelate ring

Cited by 9 publications

References 30 publications

Catalyst Activation with CpRh^III/Ir^III–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

Catalyst Activation with CpRh^III/Ir^III–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

Half-Sandwich Rhodium/Iridium(III) Complexes Designed with Cp* and 1,2-Bis(phenylchalcogenomethyl)benzene as Catalysts for Transfer Hydrogenation in Glycerol

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

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Binuclear rhodium(III) and iridium(III) monoselenocarboxylates: Synthesis, spectroscopy and structure of an ortho-metallated iridium complex featuring an IrCCC(μ-Se) chelate ring

Cited by 9 publications

References 30 publications

Catalyst Activation with Cp*RhIII/IrIII–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp* andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

Catalyst Activation with Cp*RhIII/IrIII–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp* andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

Half-Sandwich Rhodium/Iridium(III) Complexes Designed with Cp* and 1,2-Bis(phenylchalcogenomethyl)benzene as Catalysts for Transfer Hydrogenation in Glycerol

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

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Catalyst Activation with CpRh^III/Ir^III–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation

Catalyst Activation with CpRh^III/Ir^III–1,2,3-Triazole-Based Organochalcogen Ligand Complexes: Transfer Hydrogenation via Loss of Cp andN-MethylmorpholineN-Oxide Based vs Oppenauer-Type Oxidation