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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Kilian, Petr
University of St Andrews
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (12/12 displayed)
- 2021Synthetic and structural study of peri -substituted phosphine-arsinescitations
- 2021Synthetic and structural study of peri-substituted phosphine-arsinescitations
- 2021Synthetic and structural study of peri-substituted phosphine-arsinescitations
- 2019A study of through-space and through-bond JPP coupling in a rigid nonsymmetrical bis(phosphine) and its metal complexescitations
- 2018A study of through-space and through-bond JPP coupling in a rigid nonsymmetrical bis(phosphine) and its metal complexescitations
- 2018A study of through-space and through-bond J PP coupling in a rigid nonsymmetrical bis(phosphine) and its metal complexescitations
- 2016Varying the flexibility of the aromatic backbone in half sandwich rhodium(III) dithiolato complexes:a synthetic, spectroscopic and structural investigationcitations
- 2016Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligandscitations
- 2016Varying the flexibility of the aromatic backbone in half sandwich rhodium(III) dithiolato complexescitations
- 2016Varying the flexibility of the aromatic backbone in half sandwich rhodium(III) dithiolato complexes : a synthetic, spectroscopic and structural investigationcitations
- 2015Rhodium(III) and iridium(III) half-sandwich complexes with tertiary arsine and stibine ligandscitations
- 2003Phosphorus-selenium heterocycles from the tetraphospholane (PhP) 4 CH 2
Places of action
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article
A study of through-space and through-bond JPP coupling in a rigid nonsymmetrical bis(phosphine) and its metal complexes
Abstract
A series of representative late d-block metal complexes bearing a rigid bis(phosphine) ligand, <i>i</i>Pr<sub>2</sub>P-Ace- PPh<sub>2</sub> (<b>L</b>, Ace = acenaphthene-5,6-diyl), was prepared and fully characterised by various techniques, including multinuclear NMR and single crystal X-ray diffraction. The heteroleptic nature of the peri- substituted ligand <b>L</b> allows for the direct observation of the <i>J</i><sub>PP</sub> couplings in the <sup>31</sup>P{<sup>1</sup>H} NMR spectra. Magnitudes of <i>J</i><sub>PP</sub> are correlated with the identity and geometry of the metal, and the distortions of the ligand <b>L</b>. The forced overlap of the phosphine lone pairs due to the constraints imposed by the rigid acenaphthene skeleton in <b>L</b> results in large <sup>4</sup><i>J</i><sub>PP</sub> of 180 Hz. Sequestration of the lone pairs, either <i>via</i> oxidation of the phosphine, or metal chelation, results in distinct changes in the magnitude of J<sub>PP</sub>. For tetrahedral <i>d</i><sup>10</sup> complexes (<b>[LMCl2]</b>, M = Zn, Cd, Hg), the JPP is comparable or larger (193–309 Hz) to that in free ligand <b>L</b>, although the P···P separation in these complexes is increased by <i>ca</i>. 0.4 Å (compare to free ligand <b>L</b>). The magnitude of <i>J</i><sub>PP</sub> diminishes to 26–117 Hz in square planar <i>d</i><sup>8</sup> complexes (<b>[LMX2]</b>, M = Ni, Pd, Pt, X = Cl, Br) and octahedral Mo<sup>0</sup> complex [<b>LMo(CO)4]</b>, 33 Hz). Coupling Deformation Density calculations indicate the through-space interaction dominates in free <b>L</b>, whilst in metal complexes the main coupling pathway is via the metal atom.