Triphenylphosphan‐Nickel(0)‐Komplexe mit Isocyanid‐Liganden — [(RNC)nNi(PPh3)4–n] (n = 1–3)

Wenschuh, Eberhard; Wilhelm, Dieter; Hartung, H.; Baumeister, Ute

doi:10.1002/zaac.19946201206

Cited by 8 publications

(9 citation statements)

References 9 publications

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“…63 In clear contrast, addition of 1 equiv. The identity of this Ni(0) product has been established unequivocally through independent synthesis from Ni(COD) 2 , 2 equiv.…”

Section: Chemical Properties Of Dinickel Coresmentioning

confidence: 98%

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

et al. 2015

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Binuclear complexes of Ni(i) have been prepared from a 4-terphenyldithiophenol ligand. Steric effects were found to determine the formation of coordination isomeric structures that differ in the nature of metal-to-ligand bonding. Coordination of spatially demanding phosphine ligands PR3, R = C6H6, C6H11, at nickel sites results in a butterfly shaped thiolate-bridged Ni2(μ-S)2 motif. For smaller PMe3, the central π-system of the 4-terphenyl backbone adopts a bis-allyl like μ-syn-η(3):η(3)-C6H4 structure due to significant d-π* Ni(i)-to-ligand charge transfer. Delocalisation indices δ(Ni-Ni) derived from DFT calculations provide a metric to assess the strength of electronic coupling of the Ni sites based on solid state structural data, and indicated less strong electronic coupling for the bis-allyl like structure with δ(Ni-Ni) = 0.225 as compared to 0.548 for the Ni2(μ-S)2 structural motif. A qualitative reactivity study toward CNCH3 as an auxiliary ligand has provided the first insight into the chemical properties of the bimetallic complexes presented.

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“…63 In clear contrast, addition of 1 equiv. The identity of this Ni(0) product has been established unequivocally through independent synthesis from Ni(COD) 2 , 2 equiv.…”

Section: Chemical Properties Of Dinickel Coresmentioning

confidence: 98%

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

et al. 2015

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“…Although the Sb-Ni distance in 4 (2.6253(4) ) is 0.17 longer than that measured in 1, the observed arrangement of the two moieties supports the presence of a direct Ni!Sb interaction. [10] In support of this view, the n (CN) of 4 (2142 cm À1 ), which is considerably higher than that found in (CyNC)Ni(PPh 3 ) 3 (2020 cm À1 ), [14] shows that the transfer of electron density from nickel to antimony reduces the metallobasicity of the nickel atom and thus the strength of the Ni!isocyanide p-backbonding interaction. A similar effect has been observed by Figueroa upon coordination of a Lewis acidic thallium cation to isocyanide nickel(0) complexes.…”

mentioning

confidence: 95%

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

2014

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According to the covalent bond classification (CBC) method, two-electron donors are defined as L-type ligands, one-electron donors as X-type ligands, and two-electron acceptors as Z-type ligands. These three ligand functions are usually associated to the nature of the ligating atom, with phosphine, alkyl, and borane groups being prototypical examples of L-, X- and Z-ligands, respectively. A new SbNi platform is reported in which the ligating Sb atom can assume all three CBC ligand functions. Using both experimental and computational data, it is shown that PhICl2 oxidation of (o-(Ph2P)C6H4)3SbNi(PPh3) (1) into [(o-(Ph2P)C6H4)3ClSb]NiCl (2) is accompanied by a conversion of the stibine L-type ligand of 1 into a stiboranyl X-type ligand in 2. Furthermore, the reaction of 2 with the catecholate dianion in the presence of cyclohexyl isocyanide results in the formation of [(o-(Ph2P)C6H4)3(o-O2C6H4Sb)]Ni(CNCy) (4), a complex featuring a nickel atom coordinated by a Lewis acidic, Z-type, stiborane ligand.

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“…Although the Sb‐Ni distance in 4 (2.6253(4) Å) is 0.17 Å longer than that measured in 1 , the observed arrangement of the two moieties supports the presence of a direct Ni→Sb interaction 10. In support of this view, the ν (CN) of 4 (2142 cm −1 ), which is considerably higher than that found in (CyNC)Ni(PPh 3 ) 3 (2020 cm −1 ),14 shows that the transfer of electron density from nickel to antimony reduces the metallobasicity of the nickel atom and thus the strength of the Ni→isocyanide π‐backbonding interaction. A similar effect has been observed by Figueroa upon coordination of a Lewis acidic thallium cation to isocyanide nickel(0) complexes 15.…”

Section: Methodsmentioning

confidence: 70%

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

2014

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According to the covalent bond classification (CBC) method, two‐electron donors are defined as L‐type ligands, one‐electron donors as X‐type ligands, and two‐electron acceptors as Z‐type ligands. These three ligand functions are usually associated to the nature of the ligating atom, with phosphine, alkyl, and borane groups being prototypical examples of L‐, X‐ and Z‐ligands, respectively. A new SbNi platform is reported in which the ligating Sb atom can assume all three CBC ligand functions. Using both experimental and computational data, it is shown that PhICl2 oxidation of (o‐(Ph2P)C6H4)3SbNi(PPh3) (1) into [(o‐(Ph2P)C6H4)3ClSb]NiCl (2) is accompanied by a conversion of the stibine L‐type ligand of 1 into a stiboranyl X‐type ligand in 2. Furthermore, the reaction of 2 with the catecholate dianion in the presence of cyclohexyl isocyanide results in the formation of [(o‐(Ph2P)C6H4)3(o‐O2C6H4Sb)]Ni(CNCy) (4), a complex featuring a nickel atom coordinated by a Lewis acidic, Z‐type, stiborane ligand.

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Triphenylphosphan‐Nickel(0)‐Komplexe mit Isocyanid‐Liganden — [(RNC)_nNi(PPh₃)_4–n] (n = 1–3)

Cited by 8 publications

References 9 publications

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

Binuclear complexes of Ni(i) from 4-terphenyldithiophenol

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

Redox and Anion Exchange Chemistry of a Stibine–Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element

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