Rhenium(V) Complexes with Selenolato‐ and Tellurolato‐Substituted Schiff Bases – Released PPh<sub>3</sub>as a Facile Reductant

Jungfer, Maximilian Roca; Hagenbach, Adelheid; Lang, Ernesto Schulz; Abram, Ulrich

doi:10.1002/ejic.201901092

Cited by 8 publications

(30 citation statements)

References 74 publications

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“…This is in contrast to the instability of rhenium(V) complexes with the same ligands we reported earlier. [ 30 ] Similarly to the reported rhenium complexes, the 77 Se signals of the selenolato ligands appear between 197 and 326 ppm and the corresponding 125 Te resonances are found between 300 and 477 ppm. The shielding of the chalcogen atoms decreases in the order Pd > Ni > Pt, which has been observed in Schiff base selenolato complexes before.…”

Section: Resultssupporting

confidence: 72%

“…[NiCl 2 (PPh 3 ) 2 ], [63] [Pd(OAc) 2 ], [64] [Pd(OAc) 2 (PPh 3 ) 2 ], [64] [PtCl 2 (PPh 3 ) 2 ], [65][66][67] {HL Se } 2 , [30] {HL Te } 2 , [30] bis(2-aminophenyl) diselenide and bis-(2-aminophenyl)ditelluride were prepared according to literature procedures. [68][69][70] All other chemicals were reagent grade and used as received.…”

Section: Methodsmentioning

confidence: 99%

“…The reduction of the salicylidene Schiff bases of bis(2-aminophenyl)diselenide and -telluride was performed in situ by released PPh 3 ligands from the oxido-and arylimidorhenium(V) starting materials. [30,31] This methods represents a considerable progress over the hitherto occasionally use of metal(0) species. [32] In the present work, we demonstrate that the method used for high-valent rhenium complexes can be extended to the metals nickel, palladium and platinum.…”

Section: Introductionmentioning

confidence: 99%

“…The packing Table 1. Selected bond lengths [Å] and angles (°) in the dichalcogenides {HL Y } 2 [30] and their nickel, palladium and platinum complexes [M(L Y )(PPh 3 )] (Y = Se, Te). [21,[25][26][27][28][29]34,[36][37][38] and platinum [39][40][41][42][43][44][45][46][47][48][49][50][51][52] [53] Ni(TeMes)Cp(PEt 3 ), [54] [W(CO) 5 -μ-(TePh)NiCp(PPh 3 )] [55] and [57] [(NiCpiPr 4 ) 2 -μ-( Te) 2 ] (2.44-2.45 Å), [58] [CpFe(C 5 H 4 )-Te(I) 2 -Ni(NHC)Cp] (2.4407(8) Å) [59] and (μ 4 -telluro)-hexakis(μ 3 -telluro)bis(μ 2 -bis(diphenylphosphino)methane)-bis(η 5 -tert-butylcyclopentadienyl)-pentanickeldiniobium (2.436(5) Å) [60] show the overall shortest Ni-Te bond lengths.…”

Section: Introductionmentioning

confidence: 99%

“…This is not unexpected, since such species are also present in the fragmentation patterns of the rhenium complexes, we have studied recently. [30] The yields reported in the Experimental Section are in the range between 55 and 80 per cent and refer to the isolated pure compounds. But it should be mentioned that the reaction conditions had to be optimized for parameters such as solvent, temperature and reaction time for each individual complex.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

2020

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The salicylidene Schiff bases of bis(2-aminophenyl)diselenide and-ditelluride react with [M II Cl 2 (PPh 3) 2 ] (M = Ni, Pt) or [Pd II (OAc) 2 (PPh 3) 2 ] with formation of square-planar complexes with the general formulae [M II (L Y)(PPh 3)] (M = Ni, Pd, Pt, Y = Se, Te). The ligands coordinate to the metals as tridentate {O,N,Se/Te} chelates. The reduction of the dichalcogenides and the formation of the chalcogenolato ligands occurs in situ by released PPh 3 ligands. A mechanism for such reactions has been [a

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Section: Resultssupporting

confidence: 72%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

2020

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Oxidorhenium(V) and Rhenium(III) Complexes with Arylselenolato and ‐tellurolato Ligands

et al. 2023

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In situ prepared lithium arylselenolates {LiSePh, LiSe(2,6-Me 2 Ph), LiSe(2,4,6-Me 3 Ph)} or -tellurolates {LiTePh, LiTe(2,6-Me 2 Ph), LiTe(2,4,6-Me 3 Ph)} react with [ReOCl 3 (PPh 3 ) 2 ] and (NBu 4 )Br in good yields under formation of rhenium(V) complexes of the composition (NBu 4 )[ReO(L) 4 )]. The first oxidorhenium(V) complex with four monodentate phenolato ligands, [ReO(2,6-Me 2 Ph) 4 ] À , was prepared and isolated in crystalline form. This allows a comparison of experimental and computational data of a full series of such compounds with basal O, S, Se and Te donor atoms. Similar reactions with [ReCl 3 (PPh 3 ) 2 (CH 3 CN)] or [ReCl 3 (PMe 2 Ph) 3 ] give trigonal bipyramidal rhenium(III) complexes of the compositions [Re(PPh 3 )(L) 3 (CH 3 CN)] or [Re-(PPh 3 ) 2 (L) 3 ] depending on the chalcogenolate applied. The reported oxidorhenium(V) and rhenium(III) complexes were fully characterized by spectroscopic methods and X-ray diffraction. The bonding situation in the rhenium(V) and rhenium(III) chalcogenolates was assessed through density functional theory calculations based on the quantum theory of atoms in molecules (QTAIM), natural bonding orbital (NBO) analysis, charge analysis, the electron localization function (ELF) maps and topological descriptors at the {3,À 1} critical points such as metallicities. Expectedly, the ionicity of the rhenium-chalcogen bonds decreases according to all three applied charge models from O to Te. Generally, the ReÀ Se and ReÀ Te bonds are more directional in the Re(III) complexes than in the oxidorhenium(V) compounds.

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Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

2022

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Structurally variable organochalcogen clusters containing palladium(II) and nickel(II) ions were assembled starting from the salicylidene-substituted dichalcogenides (Y–C6H4–NCH–C6H4–OH)2 ({HLY}2, where Y = Se or Te), and palladium or nickel acetate. The tetrameric palladium clusters contain reduced chalcogenolato ligands {Y–C6H4–NCH–C6H4–O)}2– ({L′Y}2–, where Y = Se or Te), while the initially formed trimeric nickel clusters contain the intact, coordinated dichalcogenides. The palladium clusters have a general formula of [Pd4(L′Y)4] and represent the first examples of palladium complexes where both a gyrobifastigial and a pseudocubane arrangement of the central Pd4Y4 unit could be established with the same ligand, only depending on the solvents used for crystallization. Reduced density gradient (RDG) considerations based on density functional theory calculations suggest that the commonly referred to stabilizing chalcogen–palladium or palladium–palladium interactions for the two geometric arrangements are weak van der Waals contacts resulting from the contact of two nonbinding lone pairs. In the case of the pseudocubane arrangement, a repulsive steric effect, which is indicated by RDG analysis, is clearly supported by the cuplike distortions detected in the solid-state structure of the compound. In contrast to the reactions with palladium acetate, where the dichalcogenides were cleaved, during similar reactions with nickel acetate, the dichalcogenides remained intact and trimeric clusters of the composition [Ni-μ2-κ2-(Ni{κ5-LY}2)2-μ2-(OAc)2] (Y = Se, Te) were formed. Air oxidation and hydrolysis of [Ni-μ2-κ2-(Ni{κ5-LTe}2)2-μ2-(OAc)2] gave a rare example of a hexanuclear nickel cluster of the composition [Ni2-κ5-(Ni4-κ6-μ6-{(L′Te 2O3)(L′TeO2)2}2)-μ2-(H2O)2], which is composed of a well-defined framework consisting of tellurinic anhydride and tellurinate units, which proves the comparably higher oxidation sensitivity of the trinickel dichalcogenide complexes. Electron spray ionization mass spectrometry spectra of both the palladium and nickel clusters indicate that they show fluctional behavior with varying nuclearity in solution and can adopt multiple charge states especially because of the noninnocence of the chalcogen-based ligands. The complexes were fully characterized by spectroscopic methods, elemental analyses, and X-ray diffraction.

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Rhenium(V) Complexes with Selenolato‐ and Tellurolato‐Substituted Schiff Bases – Released PPh₃as a Facile Reductant

Cited by 8 publications

References 74 publications

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

Oxidorhenium(V) and Rhenium(III) Complexes with Arylselenolato and ‐tellurolato Ligands

Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

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Rhenium(V) Complexes with Selenolato‐ and Tellurolato‐Substituted Schiff Bases – Released PPh3as a Facile Reductant

Cited by 8 publications

References 74 publications

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

Oxidorhenium(V) and Rhenium(III) Complexes with Arylselenolato and ‐tellurolato Ligands

Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

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Rhenium(V) Complexes with Selenolato‐ and Tellurolato‐Substituted Schiff Bases – Released PPh₃as a Facile Reductant