A C3v-symmetrical tribenzotriquinacene-based threefold N-heterocyclic carbene. Coordination to rhodium(i) and stereoelectronic properties

Segarra, Candela; Linke, Jens; Mas‐Marzá, Elena; Kuck, Dietmar; Peris, Eduardo

doi:10.1039/c3cc46155f

Cited by 27 publications

(13 citation statements)

References 40 publications

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“…[4][5][6][7] Chemically,t he four bridgehead positions and the six outer positions of the aromatic periphery can be functionalized independently and in various ways and the electronic interaction of the three benzene units is negligible.…”

Section: Thepolycyclicmolecularframeworkoftribenzotriquinacenementioning

confidence: 99%

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

et al. 2015

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Inherently chiral acetophenones and benzaldehydes bearing the large, bowl-shaped framework of tribenzotriquinacene (TBTQ) were synthesized in enantiomerically pure form employing enzyme catalysis. Five-step sequences involving lipase CAL-B lead to the (M)-enantiomers, (+)-2-acetyl-TBTQ (M)-5 and (+)-2-formyl-TBTQ (M)-6, whereas use of lipase PS leads to the (P)-enantiomers, (-)-2-acetyl-TBTQ (P)-5 and (-)-2-formyl-TBTQ (P)-6, with at least 99% ee in each case. The absolute configuration of these rigid 3D building blocks was determined by X-ray diffraction analysis of the ketones 5 and by comparison of their chiroptical properties with those of the aldehydes 6.

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Section: Thepolycyclicmolecularframeworkoftribenzotriquinacenementioning

confidence: 99%

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

et al. 2015

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“…[15] Both complexes were fully characterized by NMR, IR, and UV/Vis spectroscopy,elemental microanalysis, and X-ray crystallography. After short work-up procedures, 2a and 2h can be isolated in analytically pure form in 73 %a nd 66 %y ield, respectively.T hey are fully soluble in chlorinated solvents and partially in THF.T hey show ah igh stability toward air and moisture both in solution and in the solid state.…”

Section: Synthetic Aspectsmentioning

confidence: 99%

Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

et al. 2015

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In computational chemistry, non-additive and cooperative effects can be defined in terms of a (differential) many-body expansion of the energy or any other physical property of the molecular system of interest. One-body terms describe energies or properties of the subsystems, two-body terms describe non-additive but pairwise contributions and three-body as well as higher-order terms can be interpreted as a measure for cooperativity. In the present article, this concept is applied to the analysis of ultraviolet/visible (UV/Vis) spectra of homotrinuclear transition-metal complexes by means of a many-body expansion of the change in the spectrum induced by replacing each of the three transition-metal ions by another transition-metal ion to yield a different homotrinuclear transition-metal complex. Computed spectra for the triangulo-complexes [M3 {Si(mt(Me) )3}2] (M=Pd/Pt, mt(Me) =methimazole) and tritopic triphenylene-based N-heterocyclic carbene Rh/Ir complexes illustrate the concept, showing large and small differential three-body cooperativity, respectively.

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“…On several occasions their activity has proven higher than the activities shown by their monometallic counterparts [ 23 , 26 ]. In the last few years we became interested in the design of several types of C 3v -symmetric tris-NHCs, both for the preparation of self-assembly molecular cages [ 12 – 13 27 ] and for the design of discrete trimetallic molecules whose catalytic performances were explored [ 23 , 25 , 28 – 29 ]. Among these ligands, we found those featuring a nanoscale distance between the metals especially interesting [ 13 , 27 ] because for these systems a catalytic cooperation between the active metal sites should not be expected.…”

Section: Introductionmentioning

confidence: 99%

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

Mejuto¹,

Royo²,

Guisado‐Barrios³

et al. 2015

Beilstein J. Org. Chem.

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SummaryThe coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD)] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene) complex with three [IrCl(CO)2] fragments, allowed the estimation of the Tolman electronic parameter (TEP) for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones.

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A C3v-symmetrical tribenzotriquinacene-based threefold N-heterocyclic carbene. Coordination to rhodium(i) and stereoelectronic properties

Cited by 27 publications

References 40 publications

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

Enantiomerically Pure Tribenzotriquinacenes through Stereoselective Synthesis

Differential Many‐Body Cooperativity in Electronic Spectra of Oligonuclear Transition‐Metal Complexes

Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

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