Iodide [(η5-indenyl)IrI2]n: an effective precursor to (indenyl)iridium sandwich complexes

Chamkin, Aleksandr A.; Finogenova, Anastasiia M.; Nelyubina, Yulia V.; Laskova, Julia; Kudinov, Alexander R.; Loginov, Dmitry A.

doi:10.1016/j.mencom.2016.11.010

Cited by 16 publications

(4 citation statements)

References 30 publications

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“…The indenyl ligand in these complexes is almost planar; the hinge angles , are 0.1, 3.2, and 3.5°, respectively. At the same time, the slip parameter, ,, which is used to describe the slip-fold distortion in the indenyl complexes, has a considerably higher value for the hexamethylbenzene derivative [ 2e ](SbF 6 ) 2 (0.13 Å) in comparison with other complexes (0.07 for [ 2g ](SbF 6 ) 2 and [ 3 ](SbF 6 ) 4 ), which can be expected from the higher steric hindrance of hexamethylbenzene.…”

Section: Resultssupporting

confidence: 57%

Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination

et al. 2018

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An efficient protocol for synthesis of indenyl rhodium complexes with arene ligands has been developed. The hexafluoroantimonate salts [(η5-indenyl)Rh(arene)](SbF6)2 (arene = benzene (2a), o-xylene (2b), mesitylene (2c), durene (2d), hexamethylbenzene (2e), and [2.2]paracyclophane (2g)) were obtained by iodide abstraction from [(η5-indenyl)RhI2] n (1) with AgSbF6 in the presence of benzene and its derivatives. The procedure is also suitable for the synthesis of the dirhodium arene complex [(μ-η:η′-1,3-dimesitylpropane){Rh(η5-indenyl)}2](SbF6)4 (3) starting from 1,3-dimesitylpropane. The structures of [2e](SbF6)2, [2g](SbF6)2, and [3](SbF6)4 were determined by X-ray diffraction. The last species has a sterically unfavorable conformation, in which the bridgehead carbon atoms of the indenyl ligand are arranged close to the propane linker between two mesitylene moieties. Experimental and DFT calculation data revealed that the benzene ligand in 2a is more labile than that in the related cyclopentadienyl complexes [(C5R5)Rh(C6H6)]2+. Complex 2c effectively catalyzes the reductive amination reaction between aldehydes and primary (or secondary) amines in the presence of carbon monoxide, giving the corresponding secondary and tertiary amines in very high yields (80–99%). This protocol is the most active in water.

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Section: Resultssupporting

confidence: 57%

Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination

et al. 2018

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“…[CpIrI 2 ] n ,24 [(η 5 -indenyl)-RhI 2 ] n , 2b and [(η 5 -indenyl)IrI 2 ] n25 were prepared as described in the literature. All other reagents were purchased from Acros or Aldrich and used as received.…”

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confidence: 71%

“…The signals of indenyl and fluorene systems in the NMR spectra and X-ray diffraction data were assigned according to the IUPAC recommendation (Scheme ). Starting materials [Cp*CoI 2 ] 2 , [CpRhI 2 ] n , [CpIrI 2 ] n , [(η 5 -indenyl)RhI 2 ] n , and [(η 5 -indenyl)IrI 2 ] n were prepared as described in the literature. All other reagents were purchased from Acros or Aldrich and used as received.…”

Section: Methodsmentioning

confidence: 99%

Fluorene Complexes of Group 9 Metals: Fluorene Effect and Application for Reductive Amination

et al. 2019

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The η 6 -fluorene cyclopentadienyl complexes [(η 5 -C 5 R 5 )-M(η 6 -fluorene)](SbF 6 ) 2 (1: M = Co, R = Me; 2a: M = Rh, R = H; 2b: M = Ir, R = H) were synthesized by the iodide abstraction from [(η 5 -C 5 R 5 )MI 2 ] n with AgSbF 6 in the presence of fluorene. The procedure is also suitable for the synthesis of the indenyl derivatives [(η 5indenyl)M(η 6 -fluorene)](SbF 6 ) 2 (3a: M = Rh; 3b: M = Ir) starting from [(η 5 -indenyl)MI 2 ] n . The structures of [1](SbF 6 ) 2 and [2b](SbF 6 ) 2 were determined by X-ray diffraction. The rhodium complex [2a]-(SbF 6 ) 2 readily undergoes the replacement of the fluorene ligand by mesitylene, being more reactive than the benzene derivative [CpRh(η 6 -C 6 H 6)](SbF 6 ) 2 . According to experimental data and DFT calculations, the fluorene elimination proceeds via a cascade of η 6 → η 5 → η 1 haptotropic rearrangements. The complex [2b](SbF 6 ) 2 (at 1 mol % loading) effectively catalyzes the reductive amination reaction between aldehydes (or ketones) and primary aromatic (or secondary aliphatic) amines in the presence of carbon monoxide, giving the corresponding secondary and tertiary amines in the range of yields 59−91%. This protocol uses water as a solvent.

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“…The third most populated area (type 3 stacking) is the one with stacking at large horizontal displacements of uncoordinated six-membered rings (Figure ), with r x = 4.5–5.0 Å (Figure ). This stacking can be with r y = 7.0–7.5 Å (Figure ) and normal distances of R = 2.0–2.5 Å (Figure ), as in the crystal structure AGONER01 (Figure ). However, it can also be with larger offset r y = 8.0–8.5 Å (Figure ) and even smaller normal distances of R = 1.0–1.5 Å (Figure ), as in the crystal structure GACTAG (Figure ).…”

Section: Resultsmentioning

confidence: 78%

Stacking Interactions between Indenyl Ligands of Transition Metal Complexes: Crystallographic and Density Functional Study

Malenov

Zarić

2020

Crystal Growth & Design

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The analysis of crystal structures deposited in the Cambridge Structural Database showed that indenyl ligands of transition metal complexes prefer to form stacking interactions with one of the three geometries: two of them (types 1 and 2) at small horizontal displacements and one (type 3) at large horizontal displacements. DFT calculations on several model molecules showed that types 1 and 2 are minima at potential energy surfaces, with substantial interaction energies that surpass -8.0 kcal/mol. Type 3 has small energy contribution (around -2.0 kcal/mol) to the stability of supramolecular structures, however, it is combined with simultaneous stronger stacking or aromatic C-H/π interactions. Stacking of indenyl ligands is significantly stronger than the stacking of corresponding cyclopentadienyl ligands (-3.0 kcal/mol), due to larger size of

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Iodide [(η5-indenyl)IrI2]n: an effective precursor to (indenyl)iridium sandwich complexes

Cited by 16 publications

References 30 publications

Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination

Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination

Fluorene Complexes of Group 9 Metals: Fluorene Effect and Application for Reductive Amination

Stacking Interactions between Indenyl Ligands of Transition Metal Complexes: Crystallographic and Density Functional Study

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