Dimethylformamide as a convenient CO source for the facile preparation of rhodium-, iridium- or ruthenium-chlorocarbonyl complexes directly from RhCl3·3H2O, IrCl3·3H2O or RuCl3·3H2O

Serp, Philippe; Hernandez, Marc; Kalck, Philippe

doi:10.1016/s1387-1609(00)88534-5

Cited by 3 publications

(2 citation statements)

References 8 publications

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“…Indeed a solvent like DMF has previously been used as a convenient source of CO in organic reactions 22 or for the preparation of chlorocarbonyl complexes of Ir, Ru or Rh. 23 The deshielded doublet signal lying at 10.92 ppm ( 3 J = 7.9 Hz, integration 1H) is assigned to proton a lying in the deshielding cone of the second dibenzo[a,c]phenazine ligand, and the doublet signal at 9.22 ppm ( 3 J = 7.9 Hz, 1H) to proton labelled b. These signals are not so distinct in the spectrum of complex 4, indicating that the greater asymmetry of the environment produced by adjacent carbonyl and chloro ligands in 5 may explain the large chemical shift difference between the signals for protons labelled a and b.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis and properties of phosphorescent iridium(iii) complexes of delocalized ligands

Bura¹,

Retailleau²,

Indelli³

et al. 2013

Dalton Trans.

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New Ir(III) complexes involving N,C-chelating difluorophenyl-pyridine (dfppy) or dibenzo[a,c]phenazine (dbpz) ligands along with either N,N-bound 5-ethynyl-2,2'-bipyridine (e-bpy) or CO + Cl co-ligands have been obtained as [Ir(dfppy)(2)(e-bpy)]PF(6), [Ir(dbpz)(2)(e-bpy)]PF(6) and cis-[Ir(dbpz)(2)(Cl)(CO)]. A single-crystal X-ray diffraction study of cis-[Ir(dbpz)(2)(CO)Cl] has shown the Ir(III) centre to adopt a distorted octahedral coordination geometry with cis-CO/Cl and trans-N,N configurations. Pronounced π-π stacking interactions involving different dibenzo[a,c]phenazine units are evident. Electronic absorption and luminescence spectroscopy at 298 K and 77 K, along with cyclic voltammetry were used to study the three complexes. Excited state lifetimes varied from 1.4 to 2.9 μs at rt with quantum yields ranging from 10.2 to 0.7%. With 5-ethynyl-2,2'-bipyridine in the first coordination sphere, the lowest emitting state is that associated with the MLCT band, whereas in the bis-phenazine case the emission is ligand-centred. Importantly, the emission wavelength can be tuned from 552 to 640 nm by changing the conjugation length of the N,C ligand.

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Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis and properties of phosphorescent iridium(iii) complexes of delocalized ligands

Bura¹,

Retailleau²,

Indelli³

et al. 2013

Dalton Trans.

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“…Similar behaviour is found for Ir, but RuCl 3 Á3H 2 O gives [RuCl 3 (CO) 2 (dmf)] À . 159 The reaction of [RhR(C 2 H 4 )(triphos)] (R Me, Et or Ph) with white phosphorus in thf gave [Rh(Z 1 :Z 2 -P 4 R)(triphos)], the ¢rst example of converting P 4 into a P^C bond using a transition metal complex. 160 The Tp derivative HB(2,4-Cl 2 -3,5-Me 2 pz) 3 (L) forms [RhL(CO)(PMePh 2 ) 2 ], with only one N atom bonded to Rh, but it also has an agostic B^H^Rh bond.…”

Section: Low Oxidation Statesmentioning

confidence: 99%

16 The noble metals

Thornton¹

2000

Annu. Rep. Prog. Chem., Sect. A

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Structural Study of Model Rhodium(I) Carbonylation Catalysts Activated by Indole-2-/Indoline-2-Carboxylate Bidentate Ligands and Kinetics of Iodomethane Oxidative Addition

et al. 2022

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The rigid-backbone bidentate ligands Indoline-2-carboxylic acid (IndoliH) and Indole-2-carboxylic acid (IndolH) were evaluated for rhodium(I). IndoliH formed [Rh(Indoli)(CO)(PPh3)] (A2), while IndolH yielded the novel dinuclear [Rh1(Indol’)(CO)(PPh3)Rh2(CO)(PPh3)2] (B2) complex (Indol’ = Indol2−), which were characterized by SCXRD. In B2, the Rh1(I) fragment [Rh1(Indol’)(CO)(PPh3)] (bidentate N,O-Indol) exhibits a square-planar geometry, while Rh2(I) shows a ‘Vaska’-type trans-[O-Rh2(PPh3)2(CO)] configuration (bridging the carboxylate ‘oxo’ O atom of Indol2−). The oxidative addition of MeI to A2 and B2 via time-resolved FT-IR, NMR, and UV/Vis analyses indicated only Rh(III)-alkyl species (A3/B3) as products (no migratory insertion). Variable temperature kinetics confirmed an associative mechanism for A2 via an equilibrium-based pathway (ΔH≠ = (21 ± 1) kJ mol−1; ΔS≠ = (−209 ± 4) J K−1mol−1), with a smaller contribution from a reverse reductive elimination/solvent pathway. The dinuclear complex B2 showed the oxidative addition of MeI only at Rh1(I), which formed a Rh(III)-alkyl, but cleaved the bridged Rh2(I) site, yielding trans-[RhI(PPh3)2(I)(CO)] (5B) as a secondary product. A significantly smaller negative activation entropy [ΔH≠ = (73.0 ± 1.2) kJ mol−1; ΔS≠ = (−21 ± 4) J K−1mol−1] via a more complex/potential interchange mechanism (the contribution of ΔS≠ to the Gibbs free energy of activation, ΔG≠, only ±10%) was inferred, contrary to the entropy-driven oxidative addition of MeI to A2 (the contribution of ΔS≠ to ΔG≠ ± 75%).

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Dimethylformamide as a convenient CO source for the facile preparation of rhodium-, iridium- or ruthenium-chlorocarbonyl complexes directly from RhCl3·3H2O, IrCl3·3H2O or RuCl3·3H2O

Cited by 3 publications

References 8 publications

Synthesis and properties of phosphorescent iridium(iii) complexes of delocalized ligands

Synthesis and properties of phosphorescent iridium(iii) complexes of delocalized ligands

16 The noble metals

Structural Study of Model Rhodium(I) Carbonylation Catalysts Activated by Indole-2-/Indoline-2-Carboxylate Bidentate Ligands and Kinetics of Iodomethane Oxidative Addition

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