Synthesis and structural characterisation of the phenyl/scorpionate hybrid ligand [Ph(pz)BC5H10]−

Kunz, Kerstin; Blasberg, Florian; Bolte, Michael; Lerner, Hans‐Wolfram

doi:10.1016/j.ica.2009.02.002

Cited by 5 publications

(6 citation statements)

References 39 publications

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“…For comparison, the sum of the covalent radii of Tl and C sp 2 is 2.18 Å . Furthermore, the observed thallium–centroid separations of 3.04 and 3.13 Å, respectively, for 2 and 4 are within the typical thallium···centroid distances (2.85–3.18 Å) observed for other structurally characterized Tl−π-arene complexes − and similar to that noted for the mono(pyrazolyl)borate complex [Ph(Pz)BC 5 H 10 ]Tl with a thallium···centroid distance of 2.959 Å . The closest intermolecular Tl···Tl separations of 2 and 4 at 5.83 and 6.38 Å, respectively, exclude any noteworthy interactions between thallium atoms in the solid state.…”

Section: Results and Discussionsupporting

confidence: 80%

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues

Vanga,

Phan,

et al. 2023

Inorg. Chem.

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Thallium(I) complexes of B-methylated and B-phenylated tris(pyridyl)borates featuring trifluoromethyl groups at the pyridyl ring 6positions have been synthesized by metathesis using the corresponding potassium salts [MeB(6-(CF 3 )Py) 3 ]K and [PhB(6-(CF 3 )Py) 3 ]K with thallium(I) acetate. The closely related tris(pyrazolyl)borate analogue [PhB(3-(CF 3 )Pz) 3 ]Tl has also been prepared, and comparisons of structural and spectroscopic features between the two scorpionate families are presented. [MeB(6-(CF 3 )Py) 3 ]Tl displays κ 3 -coordination of the tris(pyridyl)borate similar to that of tris(pyrazolyl)borate in [MeB(3-(CF 3 )Pz) 3 ]Tl, while [PhB(6-(CF 3 )Py) 3 ]Tl and [PhB(3-(CF 3 )Pz) 3 ]Tl feature κ 2 -N,N ligand coordination modes with the B-phenyl groups flanking the thallium sites. 19 F NMR spectroscopy of [MeB(6-(CF 3 )Py) 3 ]Tl reveals the presence of a remarkably large 1208 Hz four-bond thallium−fluorine coupling constant in chloroform at room temperature, which is considerably larger than 878 Hz observed for the pyrazolyl borate analogue [MeB(3-(CF 3 )Pz) 3 ]Tl. Although [PhB(6-(CF 3 )Py) 3 ]Tl is structurally nonrigid at room temperature in chloroform, at lower temperatures, the ligand arm exchange slows down, revealing 4 J Tl−F = 1110 Hz. Steric demands of these ligands have been quantified using the buried volume concept. In addition, ligand transfer chemistry from [MeB(6-(CF 3 )Py) 3 ]Tl and [PhB(6-(CF 3 )Py) 3 ]Tl to copper(I) under ethylene and computational analyses of the various coordination modes of tris(pyrazolyl)borates and tris(pyridyl)borates are reported.

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Section: Results and Discussionsupporting

confidence: 80%

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues

Vanga,

Phan,

et al. 2023

Inorg. Chem.

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“…105 η 6 -Tl-arene interactions do not seem to be very frequent and a search in the CCDC structural database (version 5.35, updated November 2013) revealed just a couple of dozens of reported structures containing this feature. 52,[109][110][111][112][113][114][115][116][117][118][119] As in 3, the three Pt planes in 4 form an almost perfect equilateral triangle, with dihedral angles of ca. 60°.…”

Section: Reactions Of 1 and 2 With Tlpfmentioning

confidence: 99%

Preparation of Pt–Tl clusters showing new geometries. X-ray, NMR and luminescence studies

2014

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Square planar complexes [Pt(CNC)L] (CNC = C,N,C-2,6-NC5H3(C6H4-2)2; L = tht (tetrahydrothiophene, SC4H8, 1), L = CN(t)Bu (2)) react with TlPF6 in different Pt/Tl molar ratios (3/1 in the case of 1 and 1/1 in the case of 2) yielding the complexes [{Pt(CNC)(tht)}3Tl](PF6) (3) and [Pt(CNC)(CN(t)Bu)Tl](PF6) (4), respectively. The structures of 3 and 4 (X-ray) show the presence of Pt→Tl dative bonds unsupported by any bridging ligands. In complex 3, the only Tl centre is simultaneously bonded to three Pt atoms forming a perfect equilateral triangle with Pt-Tl distances of 2.9088(5) Å, remarkably short. Complex 4 is formed by three "Pt(CNC)(CN(t)Bu)Tl" units, disposed in a triangular fashion, linked together through η(6)-Tl-arene interactions, and showing Pt-Tl bonds with distances of ca. 3.04 Å. The study of these crystal structures would seem to indicate that the difference between the Pt/Tl ratios found in the complexes 3 and 4 is due to the steric requirements of the L ligand bonded to Pt. NMR studies both in solution and in the solid state show that the Pt-Tl bond persists in solutions of 3 and 4. The UV-vis spectra of 3 and 4 in solution display the same profiles as those of 1 and 2, which may suggest a partial dissociation of the Pt-Tl bond in solution. However, by DFT calculations it was proved that in this case the formation of the Pt-Tl dative bond does not produce the expected blue-shift in the UV-vis absorptions. The emissive behaviour of 1-4 in the solid state and in frozen solutions is also studied and included in this work.

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“…We therefore conclude that the attachment of anionic borate substituents may help to stabilize a broader variety of Li + -π interactions. This conclusion is supported by the solid-state structures of IV, [30] V, [31] and VI, [32] which all feature Li + -benzene π coordination ( Figure 1). In IV-VI, the desired structural motif is still enforced by a chelating side arm.…”

Section: Introductionmentioning

confidence: 62%

A Quest for Ligand‐Unsupported Li⁺–π Interactions in Mono‐, Di‐, and Tritopic Lithium Arylborates

et al. 2011

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Synthesis and structural characterisation of the phenyl/scorpionate hybrid ligand [Ph(pz)BC5H10]−

Cited by 5 publications

References 39 publications

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues

Preparation of Pt–Tl clusters showing new geometries. X-ray, NMR and luminescence studies

A Quest for Ligand‐Unsupported Li⁺–π Interactions in Mono‐, Di‐, and Tritopic Lithium Arylborates

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Synthesis and structural characterisation of the phenyl/scorpionate hybrid ligand [Ph(pz)BC5H10]−

Cited by 5 publications

References 39 publications

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues

Preparation of Pt–Tl clusters showing new geometries. X-ray, NMR and luminescence studies

A Quest for Ligand‐Unsupported Li+–π Interactions in Mono‐, Di‐, and Tritopic Lithium Arylborates

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A Quest for Ligand‐Unsupported Li⁺–π Interactions in Mono‐, Di‐, and Tritopic Lithium Arylborates