NMR studies on interaction of rhodium(II) tetratrifluoroacetate with the ligands containing nitrile, isonitrile, isothiocyanate or isocyanate functional groups

Cmoch, Piotr; Jaźwiński, Jarosław

doi:10.1016/j.molstruc.2008.10.003

Cited by 9 publications

(8 citation statements)

References 28 publications

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“…The complexation properties of dirhodium tetracarboxylates have been utilised in numerous areas, in organic chemistry, in spectroscopy of chiral organic compounds and in biology and medicine. In our previous works, we explored the complexation of rhodium tetracarboxylates with organic ligand such as amines, azoles and derivatives of pyridine, nitriles and isonitriles using NMR techniques . Our investigations were mainly focused on the formation of adducts in situ in CDCl 3 solution.…”

Section: Introductionmentioning

confidence: 99%

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Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance ¹³C and ¹⁵N CPMAS NMR investigations

Jaźwiński

Kamieński

Sadlej

2013

Magnetic Reson in Chemistry

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Complexation properties of dimeric rhodium(II) tetracarboxylates have been utilised in chemistry, spectroscopy and organic synthesis. Particularly, the combination of these rhodium salts with multifunctional ligands results in the formation of coordination polymers, and these are of interest because of their gas-occlusion properties. In the present work, the polymeric adducts of rhodium(II) tetraacetate with flexible ligands exhibiting conformational variety, ethane-1,2-diamine, propane-1,3-diamine and their N,N'-dimethyl- and N,N,N',N'-tetramethyl derivatives, have been investigated by means of elemental analysis, (13)C CPMAS NMR, (15)N CPMAS NMR and density functional theory modelling. Elemental analysis and NMR spectra indicated the axial coordination mode and regular structures of (1 : 1)n oligomeric chains in the case of adducts of ethane-1,2-diamine, N,N'-dimethylethane-1,2-diamine N,N,N',N'-tetramethylethane-1,2-diamine and N,N,N',N'-tetramethylpropane-1,3-diamine. Propane-1,3-diamine and N,N'-dimethylpropane-1,3-diamine tended to form heterogeneous materials, composed of oligomeric (1 : 1)n chains and the additive of dirhodium units containing equatorially bonded ligands. Experimental findings have been supported by density functional theory modelling of some hypothetical structures and gauge-invariant atomic orbital calculations of NMR chemical shifts.

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Section: Introductionmentioning

confidence: 99%

“…In our previous works, we explored the complexation of rhodium tetracarboxylates with organic ligand such as amines, azoles and derivatives of pyridine, nitriles and isonitriles using NMR techniques. [4][5][6] Our investigations were mainly focused on the formation of adducts in situ in CDCl 3 solution.…”

Section: Introductionmentioning

confidence: 99%

Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance ¹³C and ¹⁵N CPMAS NMR investigations

Jaźwiński

Kamieński

Sadlej

2013

Magnetic Reson in Chemistry

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“… 1 H, 13 C (In parentheses) and 15 N (square brackets) chemical shifts for ligands, and complexation shifts (ppm) for the 1 : 1 adducts ( 1 ‐Rh 2 (AcO) 4 and 1 ‐Rh 2 (TFA) 4 ) or for the samples containing rhodium salt and ligand in molar ratio of 1 : 0.5. The values for 1 ‐Rh 2 (AcO) 4 , 1 ‐Rh 2 (TFA) 4 , and 2 ‐Rh 2 (TFA) 4 were taken from the work by Cmoch; the remaining data have been measured in the present work. All measurements were carried out in CDCl 3 solutions, if not marked otherwise.…”

Section: Resultsmentioning

confidence: 99%

“…Previously, we investigated the interactions of rhodium tetracarboxylates with organic ligands bearing N, O, and S atoms . Depending on experimental conditions (slow or fast ligand exchange rate on the NMR timescale), we observed either the individual signals of ligand and adduct or the signals at averaged positions.…”

Section: Introductionmentioning

confidence: 99%

“…Previously, we investigated the interactions of rhodium tetracarboxylates with organic ligands bearing N, O, and S atoms. [17][18][19][20][21][22][23] Depending on experimental conditions (slow or fast ligand exchange rate on the NMR timescale), we observed either the individual signals of ligand and adduct or the signals at averaged positions. Adducts were characterized by a parameter complexation shift, Δδ, defined as chemical shift differences between signal in adduct and corresponding signal in free ligand (depending on the authors, this parameter is also called adduct/ complex formation shift or coordination shift).…”

Section: Introductionmentioning

confidence: 99%

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Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations

Cmoch

Głaszczka

Jaźwiński

et al. 2013

Magnetic Reson in Chemistry

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Complexation of tetrakis(μ2-N,N'-diphenylformamidinato-N,N')-di-rhodium(II) with ligands containing nitrile, isonitrile, amine, hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups has been studied in liquid and solid phases using (1)H, (13)C and (15)N NMR, (13)C and (15)N cross polarisation-magic angle spinning NMR, and absorption spectroscopy in the visible range. The complexation was monitored using various NMR physicochemical parameters, such as chemical shifts, longitudinal relaxation times T1 , and NOE enhancements. Rhodium(II) tetraformamidinate selectively bonded only unbranched amine (propan-1-amine), pentanenitrile, and (1-isocyanoethyl)benzene. No complexation occurred in the case of ligands having hydroxyl, sulfhydryl, isocyanate, and isothiocyanate functional groups, and more expanded amine molecules such as butan-2-amine and 1-azabicyclo[2.2.2]octane. Such features were opposite to those observed in rhodium(II) tetracarboxylates, forming adducts with all kind of ligands. Special attention was focused on the analysis of Δδ parameters, defined as a chemical shift difference between signal in adduct and corresponding signal in free ligand. In the case of (1)H NMR, Δδ values were either negative in adducts of rhodium(II) tetraformamidinate or positive in adducts of rhodium(II) tetracarboxylates. Experimental findings were supported by density functional theory molecular modelling and gauge independent atomic orbitals chemical shift calculations. The calculation of chemical shifts combined with scaling procedure allowed to reproduce qualitatively Δδ parameters.

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Recyclable Dirhodium Catalysts Embedded in Nanoporous Surface‐Functionalized Organosilica Hosts for Carbenoid‐Mediated Cyclopropanation Reactions

et al. 2010

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Recyclable and efficient heterogeneous catalysts have been prepared by embedding dirhodium(II,II) core carboxylate complexes into the amine‐functionalized nanosized channels of a mesoporous silica host, amine–SBA‐15. Two alternative synthetic procedures for the preparation of the catalysts have been developed and adapted for the immobilization of dirhodium complexes of variable Lewis acidity. The catalytic activity of the resulting solid materials has been evaluated in model cyclopropanation reactions of styrene at variable reaction conditions (reaction substrate, temperature, time, and solvent). Importantly, the designed catalysts, which can be readily recovered and reused, display the reactivity and selectivity profiles exceeding or comparable to their homogeneous dirhodium(II) counterparts.

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NMR studies on interaction of rhodium(II) tetratrifluoroacetate with the ligands containing nitrile, isonitrile, isothiocyanate or isocyanate functional groups

Cited by 9 publications

References 28 publications

Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance ¹³C and ¹⁵N CPMAS NMR investigations

Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance ¹³C and ¹⁵N CPMAS NMR investigations

Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations

Recyclable Dirhodium Catalysts Embedded in Nanoporous Surface‐Functionalized Organosilica Hosts for Carbenoid‐Mediated Cyclopropanation Reactions

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NMR studies on interaction of rhodium(II) tetratrifluoroacetate with the ligands containing nitrile, isonitrile, isothiocyanate or isocyanate functional groups

Cited by 9 publications

References 28 publications

Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance 13C and 15N CPMAS NMR investigations

Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance 13C and 15N CPMAS NMR investigations

Adducts of nitrogenous ligands with rhodium(II) tetracarboxylates and tetraformamidinate: NMR spectroscopy and density functional theory calculations

Recyclable Dirhodium Catalysts Embedded in Nanoporous Surface‐Functionalized Organosilica Hosts for Carbenoid‐Mediated Cyclopropanation Reactions

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Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance ¹³C and ¹⁵N CPMAS NMR investigations

Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance ¹³C and ¹⁵N CPMAS NMR investigations