Square-Planar-Tetrahedral Isomerism of Nickel Halide Complexes of Diphenylalkylphosphines

Hayter, R. G.; Humiec, F.

doi:10.1021/ic50034a006

Cited by 92 publications

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“…[12] Other examples include tetrahedral to square-planar isomerism. [13] However, the present equilibrium between mononuclear and polynuclear Ni complexes with the same molecular formula appears unprecedented. The tetranuclear form is more stabilized in the case of PN th than of PN ox , as observed by 1) the Evans method and 2) the dependence of K on temperature.…”

Section: Angewandte Chemiementioning

confidence: 98%

Unprecedented Tetranuclear Complexes with 20‐Electron Ni^II Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

et al. 2007

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Complexes under pressure! The complexes [{NiCl2(PN)}4] (PN=2‐diphenylphosphinomethyl‐2‐oxazoline or ‐2‐thiazoline; see picture; Ni green, Cl pink, P orange, S yellow, N blue, C gray) have an unprecedented, centrosymmetric Ni4Cl8 core with 20‐electron metal centers and undergo pressure‐induced fragmentation into the mononuclear, square‐planar 16‐electron complexes [NiCl2(PN)], which are in equilibrium with the respective tetramer in solution.

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Section: Angewandte Chemiementioning

confidence: 98%

Unprecedented Tetranuclear Complexes with 20‐Electron Ni^II Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

et al. 2007

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“…The 1 H NMR spectra confirm the presence of several species, but line broadening precludes further assignments.. Apart from different degrees of substitution, an equilibrium between tetrahedral and square-planar conformations of an individual species might account for the complicated behavior, as has been described for [(PEtPh 2 ) 2 NiBr 2 ]. [40,41] As tetrahedral nickel() species should be paramagnetic (S ϭ 1), which might explain the poor NMR spectroscopic data, an ESR investigation of these species is planned.…”

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confidence: 99%

Investigation of the Ligand Exchange Behavior of Square‐Planar Nickel(II) Complexes by X‐ray Absorption Spectroscopy and X‐ray Diffraction

2003

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Keywords: Nickel / Ligand exchange / EXAFS spectroscopy / XANES / X-ray diffractionThe local structure of nickel and bromine in three squareplanar nickel(II) complexes [(2,2Ј-bipyridyl) (2), [(bromo)(mesityl)bis(triphenylphosphane)nickel(II) (3)] and their ligand exchange behavior towards several solvents has been determined by means of Xray Absorption Near Edge Spectroscopy (XANES), Extended X-ray Absorption Fine Structure Spectroscopy (EXAFS), Xray Diffraction (XRD), multinuclear NMR and UV/Vis spectroscopy. Several square-planar and octahedral nickel(II) complexes were prepared and spectroscopically character-

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“…Teil) sowie aus Ro È ntgenkristallstrukturanalysen. Wie fu È r Nickelkomplexe von Diphenyl-alkylphosphinen mit einem Ligand-Metall-Verha È ltnis von 2 : 1 ausfu È hrlich beschrieben[9,10], bilden sich auch bei den Reaktionen gema È û Gl. (2)und (3) sowohl diamagnetische planare als auch paramagnetische tetraedrische Komplexe.…”

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Ligandverhalten von P-funktionellen Organozinnhalogeniden: Nickel(II)-, Palladium(II)- und Platin(II)-halogenid-Komplexe mit Me2(Cl)SnCH2CH2PPh2

Baumeister

Hartung

Krug

et al. 2000

Z. anorg. allg. Chem.

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Inhaltsu È bersicht. Me 2 (Cl)SnCH 2 CH 2 PPh 2 (1) reagiert mit Nickel(II)-, Palladium(II)-und Platin(II)-halogeniden im Molverha È ltnis 2 : 1 zu den Komplexen [MX 2 {PPh 2 -CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (M = Ni, Pd, Pt; X = Cl, Br) (3±6, 9, 10) (7, 8: M = Ni; Br anstelle von Cl). Von den Nickelkomplexen wurden jeweils das planare (3, 5, 7) und das tetraedrische (4, 6, 8) Isomer isoliert und charakterisiert. In Lo È sung liegen beide Isomere im Gleichgewicht vor. Die Kristallstrukturen und NMR-Daten belegen fu È r die planaren Nikkelkomplexe 3, 5, 7 sowie [MCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9: M = Pd; 10: M = Pt) die Existenz von intra-und intermolekularen M±Hal´´´Sn-Bru È cken. Im Ligand : Metall-Verha È ltnis 3 : 1 werden die Komplexe [M Å Cl{PPh 2 CH 2 -CH 2 Sn 7 Cl 2 Me 2 }{PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (11: M = Pd; 12: M = Pt) gebildet, die als Zwitterionen vorliegen. Die Dehalogenierung von [PdCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9) mit Natriumamalgam bzw. Graphitkalium (C 8 K) fu È hrt zu den Palladacyclen cis-[Pd{PPh 2 CH 2 CH 2 SnMe 2 } 2 ] (13) und trans-[Pd(Cl)PPh 2 CH 2 CH 2 SnMe 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 }] (14). Von den Verbindungen 1, 3, 9, 11 und 12 wurden die Kristallstrukturen bestimmt. Sa È mtliche Verbindungen sind 1 H-, 31 P-und 119 Sn-NMR-spektroskopisch charakterisiert.Abstract. Me 2 (Cl)SnCH 2 CH 2 PPh 2 (1) reacts with Ni II , Pd II , and Pt II halides in molar ratio 2 : 1 forming the complexes [MX 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (M = Ni, Pd, Pt; X = Cl, Br) (3±6, 9, 10) (7, 8: M = Ni; Br instead of Cl). The nickel complexes were isolated and characterized both as the planar (3, 5, 7) and the tetrahedral (4, 6, 8) isomer. Crystal structure analyses and NMR data indicate for the planar nikkel complexes 3, 5, 7 and [MCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9: M = Pd; 10: M = Pt) the existence of intra and intermolecular M±Hal´´´Sn bridges. In a ligand : metal molar ratio of 3 : 1 the complexes [M Å Cl{PPh 2 CH 2 CH 2 Sn 7 Cl 2 Me 2 }-{PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (11: M = Pd; 12: M = Pt) are formed which represent intramolecular ion pairs. By dehalogenation of [PdCl 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 } 2 ] (9) with sodium amalgam and graphite potassium (C 8 K), respectively, the palladacycles cis-[Pd{PPh 2 CH 2 CH 2 SnMe 2 } 2 ] (13) and trans-[Pd(Cl)PPh 2 CH 2 CH 2 SnMe 2 {PPh 2 CH 2 CH 2 Sn(Cl)Me 2 }] (14) are formed. From the compounds 1, 3, 9, 11, and 12 the crystal structures are determined. All compounds are characterized by 1 H, 31 P, and 119 Sn NMR spectroscopy.

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Square-Planar-Tetrahedral Isomerism of Nickel Halide Complexes of Diphenylalkylphosphines

Cited by 92 publications

References 0 publications

Unprecedented Tetranuclear Complexes with 20‐Electron Ni^II Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

Unprecedented Tetranuclear Complexes with 20‐Electron Ni^II Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

Investigation of the Ligand Exchange Behavior of Square‐Planar Nickel(II) Complexes by X‐ray Absorption Spectroscopy and X‐ray Diffraction

Ligandverhalten von P-funktionellen Organozinnhalogeniden: Nickel(II)-, Palladium(II)- und Platin(II)-halogenid-Komplexe mit Me2(Cl)SnCH2CH2PPh2

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Square-Planar-Tetrahedral Isomerism of Nickel Halide Complexes of Diphenylalkylphosphines

Cited by 92 publications

References 0 publications

Unprecedented Tetranuclear Complexes with 20‐Electron NiII Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

Unprecedented Tetranuclear Complexes with 20‐Electron NiII Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

Investigation of the Ligand Exchange Behavior of Square‐Planar Nickel(II) Complexes by X‐ray Absorption Spectroscopy and X‐ray Diffraction

Ligandverhalten von P-funktionellen Organozinnhalogeniden: Nickel(II)-, Palladium(II)- und Platin(II)-halogenid-Komplexe mit Me2(Cl)SnCH2CH2PPh2

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Unprecedented Tetranuclear Complexes with 20‐Electron Ni^II Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation

Unprecedented Tetranuclear Complexes with 20‐Electron Ni^II Centers: The Role of Pressure and Temperature on Their Solid‐State and Solution Fragmentation