The reactivity of new (1,5-cyclooctadiene)rhodium acylpyrazolonates towards N- and P-donor ligands: X-ray structures of [Rh(1,5-COD)Qs], [Rh(1,5-COD)(phen)]Qs·0.5H2O (HQs=1-phenyl-3-methyl-4-(2-thenoyl)-pyrazol-5-one) and [Rh(1,5-COD)Br]2

Pettinari, Cláudio; Marchetti, Fábio; Cingolani, Antonella; Bianchini, Gianluca; Дроздов, А. А.; Vertlib, Vyacheslav; Troyanov, S. I.

doi:10.1016/s0022-328x(02)01122-1

Cited by 32 publications

(7 citation statements)

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“…The complex [(cod)RhI] 2 has a bent dimeric structure (Figure 2), the bending angle (the angle between the two squares along the I…I line) being equal to 96.7°. Noteworthy, the corresponding chloro and bromo analogs [(cod)RhCl] 2 [17] and [(cod)RhBr] 2 [18] are only slightly folded with bending angles 169.3 and 148.7°, respectively. The increase in bending from Cl to I is consistent with the results of ab initio calculations previously performed by Lledos and Alvarez.…”

Section: Resultsmentioning

confidence: 99%

“…All hydrogen atoms are omitted for clarity. Selected bond lengths (Å):Rh1À C4a 2.203(12), Rh1À C5a 2.191(12), Rh1À C8a 2.202(12), Rh1À C9a 2.209(12), Rh1À C9 2.165(12), Rh1À C10 2.169(12), Rh1À C11 2.176(12), Rh1À C12 2.175(12), Rh1À C13 2.186(14), Rh1À C14 2.171(12), C4aÀ C5a 1.443(19), C4aÀ C9a 1.455(17), C5aÀ C8a 1.44(2), C9À C9a 1.416(17), C9À C8a 1.433(18), C10À C11 1.410(18), C11À C12 1.406(19), C12À C13 1.44(2), C13À C14 1.40(2), C10À C14 1.430(18).…”

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Easy Access to Versatile Catalytic Systems for C−H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes

Kharitonov

Runikhina

Nelyubina

et al. 2021

Chemistry A European J

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On the basis of the 1,2,3,4-tetrahydrofluorenyl ligand, a simple approach was developed to new effective rhodium catalysts for the construction of CÀ C and CÀ N bonds. The halide compounds [(η 5 -tetrahydrofluorenyl)RhX 2 ] 2 (2 a: X = Br; 2 b: X = I) were synthesized by treatment of the bis (ethylene) derivative (η 5 -tetrahydrofluorenyl)Rh(C 2 H 4 ) 2 (1 a) with halogens. An analogous reaction of the cyclooctadiene complex (η 5 -tetrahydrofluorenyl)Rh(cod) (1 b) with I 2 is complicated by the side formation of [(cod)RhI] 2 . The reaction of 2 b with 2,2'-bipyridyl leads to cation [(η 5 -tetrahydrofluorenyl) Rh(2,2'-bipyridyl)I] + (3). The halide abstraction from 2 a,b with thallium or silver salts allowed us to prepare sandwich compounds with incoming cyclopentadienyl, dicarbollide and mesityleneligands [(η 5 -tetrahydrofluorenyl)RhCp] + (4), (η 5 -tet-rahydrofluorenyl)Rh(η-7,8-C 2 B 9 H 11 ) (5), and [(η 5 -tetrahydrofluorenyl)Rh(η-mesitylene)] 2 + (6). The structures of 1 b, 2 b • 2I 2 , 3PF 6 , 4TlI 4 , 5, and [(cod)RhI] 2 were determined by X-ray diffraction. Compounds 2 a,b efficiently catalyze the oxidative coupling of benzoic acids with alkynes to selectively give isocoumarins or naphthalenes, depending on the reaction temperature. Moreover, they showed moderate catalytic activity in other annulations of alkynes with aromatic compounds (such as benzamide, acetanilide, etc.) which proceed through CH activation. Compound 2 b also effectively catalyzes the reductive amination of aldehydes and ketones in the presence of carbon monoxide and water via water-gas shift reaction, giving amines in high yields (67-99 %).

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Easy Access to Versatile Catalytic Systems for C−H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes

Kharitonov

Runikhina

Nelyubina

et al. 2021

Chemistry A European J

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“…4-Acyl-5-pyrazolones are an exotic variation of classical β-diketonates . We are currently developing 4-acyl-5-pyrazolonates with novel functionalities and testing their coordinative ability toward several metal acceptors, − with a strategy based on systematic substitution of the peripheral groups in order to tune their steric and electronic features. − …”

Section: Introductionmentioning

confidence: 99%

Silver Coordination Chemistry of a New Versatile “Janus”-type N₂,O₂-Bichelating Donor, Formation of an Unprecedented Supramolecular Network of Binuclear Silver Building Blocks Containing a Five-Coordinate β-Diketonate, and Isolation of Unexpected Silver−Tin−Silver Heterotrimetallic Complexes from Silver Metathesis Reactions

et al. 2004

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Synthetic, spectroscopic, and single-crystal X-ray studies are reported for several complexes of silver(I) with the N(2),O(2)-bichelating Q(py) ligand (HQ(py) = 1-(2-pyridyl)-3-methyl-4-trifluoroacetylpyrazol-5-one). Direct interaction between HQ(py) and AgNO(3) in methanol, in the presence of NaOCH(3), affords derivative Ag(Q(py)), showing a polynuclear structure composed of dinuclear building blocks with two different Ag environments and two Q(py) donors differently connected. By adding neutral ligands such as PR(3) (R = Ph, Cy, C(6)H(4)-o-CH(3), C(6)H(4)-p-F, Bu(i)) to Ag(Q(py)), dinuclear Ag(Q(py))(PR(3)) derivatives have been isolated, containing bridging N(2),O-exotridentate Q(py) donors spanning a pair of AgPR(3) moieties. Reaction of Ag(Q(py))(PPh(3)) with excess PPh(3) produces the mononuclear Ag(Q(py))(PPh(3))(2) containing N(2)-chelate Q(py). Ag(Q(py)) interacts with 1,2-bis(diphenylphosphino)ethane (dppe) yielding the derivative Ag(Q(py))(dppe), having a polynuclear structure in the solid state which is seemingly disrupted in solution, with the formation of two new species, a mononuclear neutral compound and a dinuclear ionic one. By the interaction of Ag(Q(py)) with nitrogen donors L (L = imidazole (imH), 1-methylimidazole (Meim), 1-methyl-2-mercaptoimidazole (Hmimt), 1,10-phenanthroline (phen)), mononuclear species Ag(Q(py))(L) have been obtained, where Q(py) is coordinated to silver in N(2)-chelating mode. Ag(Q(py))(PPh(3))(2) reacts with SnRCl(3) (R = Ph, Bu(n)) affording heterotrimetallic [[(Ph(3)P)(2)AgCl](2)SnRCl(3)] derivatives.

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“…The presence of the cyclooctadiene ligand, which is known to undergo easy replacement by phosphine ligands, made 21 a promising precursor for the construction of triple-metallic-layer dendrimers. However, our attempts to substitute the cyclooctadiene ligand for 1,1‘-bis(diphenylphosphino)ferrocene (dppf) turned out to be unsuccessful.…”

Section: Resultsmentioning

confidence: 99%

Dendrimers Containing Two Metallic Layers. Chloride Migration from Peripheral Gold, Palladium, or Rhodium Metals to Internal Ruthenium Atoms

et al. 2005

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An efficient strategy for the synthesis of carbosilane dendrimers containing double metallic layers has been developed. The method consists of the attachment of the Ru(p-cymene)Cl2 unit to the branches of a phosphino-terminated dendrimer, followed by abstraction with AgOTf of the chloride ligands from the ruthenium and selective incorporation, through the nitrogen pyridine atom, of the bifunctional 4-pyPPh2 molecule. Finally, metalation of the resulting species with the complexes [(tht)AuCl], [PdCl(η3-2-MeC3H4)]2, and [RhCl(cod)]2 renders the targeted Ru/Au, Ru/Pd, and Ru/Rh dendrimers. An unexpected migration of the chloride ligand bonded to the peripheral metals to the internal ruthenium atoms was observed and discussed in terms of the results obtained from density functional calculations. In the case of the Ru/Au dendrimers, the different abilities for the ligand transfer process shown by the dendrimers in comparison with a mononuclear Ru/Au model compound are explained in terms of dendritic effects.

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The reactivity of new (1,5-cyclooctadiene)rhodium acylpyrazolonates towards N- and P-donor ligands: X-ray structures of [Rh(1,5-COD)Qs], [Rh(1,5-COD)(phen)]Qs·0.5H2O (HQs=1-phenyl-3-methyl-4-(2-thenoyl)-pyrazol-5-one) and [Rh(1,5-COD)Br]2

Cited by 32 publications

References 73 publications

Easy Access to Versatile Catalytic Systems for C−H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes

Easy Access to Versatile Catalytic Systems for C−H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes

Dendrimers Containing Two Metallic Layers. Chloride Migration from Peripheral Gold, Palladium, or Rhodium Metals to Internal Ruthenium Atoms

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